WO2024075472A1 - Liquid addition-curable fluorosilicone composition, fluorosilicone rubber, and molded article - Google Patents
Liquid addition-curable fluorosilicone composition, fluorosilicone rubber, and molded article Download PDFInfo
- Publication number
- WO2024075472A1 WO2024075472A1 PCT/JP2023/032998 JP2023032998W WO2024075472A1 WO 2024075472 A1 WO2024075472 A1 WO 2024075472A1 JP 2023032998 W JP2023032998 W JP 2023032998W WO 2024075472 A1 WO2024075472 A1 WO 2024075472A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- integer
- composition
- independently
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 147
- 239000007788 liquid Substances 0.000 title claims abstract description 99
- 229920005560 fluorosilicone rubber Polymers 0.000 title claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 37
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 23
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 22
- 238000007259 addition reaction Methods 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 141
- -1 3,3,3-trifluoropropyl group Chemical group 0.000 claims description 51
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 28
- 125000000962 organic group Chemical group 0.000 claims description 27
- 239000010702 perfluoropolyether Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 55
- 230000006835 compression Effects 0.000 description 31
- 238000007906 compression Methods 0.000 description 29
- 229920002379 silicone rubber Polymers 0.000 description 28
- 239000004945 silicone rubber Substances 0.000 description 26
- 238000001723 curing Methods 0.000 description 21
- 238000000465 moulding Methods 0.000 description 18
- 238000000748 compression moulding Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 229910021485 fumed silica Inorganic materials 0.000 description 8
- 238000013007 heat curing Methods 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000013006 addition curing Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002683 reaction inhibitor Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 210000002374 sebum Anatomy 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XCMSVSBUVANQIE-UHFFFAOYSA-N [SiH4].N1N=NC2=C1C=CC=C2 Chemical compound [SiH4].N1N=NC2=C1C=CC=C2 XCMSVSBUVANQIE-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 2
- NNKJLYMBVRDUEI-UHFFFAOYSA-N chloro-tris(ethenyl)silane Chemical compound C=C[Si](Cl)(C=C)C=C NNKJLYMBVRDUEI-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000004989 laser desorption mass spectroscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002731 mercury compounds Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Definitions
- the present invention relates to a liquid addition-curable fluorosilicone composition, a fluorosilicone rubber obtained by heat-curing the composition, and a molded article thereof.
- addition-cured fluorosilicone rubber compositions have been used in aircraft and vehicle rubber parts, printer parts, etc., because the cured products have excellent gasoline and oil resistance (Patent Document 1).
- Patent Document 1 the use of cured products of addition-cured fluorosilicone rubber compositions in mobile parts from the viewpoint of sebum resistance, and in sealing parts for fuel cell vehicles from the viewpoint of acid resistance, has been considered.
- the cured products of addition-cured fluorosilicone rubber compositions used in these parts are required to have low compression set and to maintain practical strength, i.e., mechanical strength.
- the development of a liquid addition-cured fluorosilicone rubber composition with excellent productivity has been desired.
- processing methods with excellent productivity include injection molding, compression molding, and injection molding using a mold, but there is a problem that liquid addition-cured fluorosilicone rubber compositions cannot be used unless they have a viscosity that can be applied to these processing methods.
- the first aspect of the present invention has been made in consideration of the above circumstances, and aims to provide a liquid addition-curable fluorosilicone composition that has good curability, retains mechanical strength, and is suitable for injection molding and the like. It also aims to provide a fluorosilicone rubber and a molded article thereof obtained by heat-curing the composition.
- the second aspect of the present invention has been made in consideration of the above circumstances, and aims to provide a liquid addition-curable fluorosilicone composition that has very good curability, excellent storage stability, and can give a fluorosilicone rubber that retains mechanical strength, and is suitable for processing with excellent productivity. It also aims to provide a fluorosilicone rubber obtained by curing the composition.
- a first aspect of the present invention provides an addition-curable fluorosilicone composition, comprising: (A) a fluorosilicone compound represented by the following general formula (1): (In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.) a vinyl group-containing organopolysiloxane having a viscosity at 25° C.
- R1 's are each independently a group selected from an alkyl group having
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group.
- the addition-curable fluorosilicone composition of the first aspect of the present invention has good curability, maintains mechanical strength, and is suitable for injection molding, etc.
- the first aspect of the present invention provides a fluorosilicone rubber that is a cured product of the above-mentioned addition-curable fluorosilicone composition.
- the fluorosilicone rubber of the first aspect of the present invention maintains good mechanical strength.
- the first aspect of the present invention provides a fluorosilicone rubber molded article, which is a molded article of the above-mentioned fluorosilicone rubber.
- the fluorosilicone rubber molded product of the first aspect of the present invention has excellent gasoline and oil resistance, making it suitable for use in aircraft and automotive rubber parts, printer parts, etc. Its sebum resistance makes it suitable for use in mobile parts, and its acid resistance makes it suitable for use in sealing parts for fuel cell vehicles.
- a liquid addition-curable fluorosilicone composition comprising: (A') a compound represented by the following general formula (1A): (In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.) an alkenyl group-containing organopolysiloxane having a viscosity at 25° C.
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention cures quickly even at relatively low temperatures, and therefore has very good curing properties while also having excellent storage stability, and can give a fluorosilicone rubber that retains its mechanical strength upon curing.
- This liquid addition-curable fluorosilicone composition is suitable as a material for highly productive processing such as casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
- the second aspect of the present invention provides a fluorosilicone rubber that is a cured product of the addition-curable fluorosilicone composition of the second aspect of the present invention.
- the fluorosilicone rubber of the second aspect of the present invention can exhibit low compression set and high mechanical strength.
- the addition-curable fluorosilicone composition of the first aspect of the present invention is liquid and cures quickly even at relatively low temperatures, resulting in good curing properties and a fluorosilicone rubber that retains its mechanical strength. Furthermore, this liquid addition-curable fluorosilicone composition is suitable as a material for casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
- liquid addition-curable fluorosilicone composition of the second aspect of the present invention cures quickly even at relatively low temperatures, and therefore has very good curing properties while also having excellent storage stability, making it possible to give a fluorosilicone rubber that retains its mechanical strength. Furthermore, this liquid addition-curable fluorosilicone composition is suitable as a material for highly productive processing such as casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
- the fluorosilicone rubber of the second aspect of the present invention can exhibit low compression set and high mechanical strength.
- the inventors conducted extensive research to achieve the above object, and discovered that by using a hydrogen polysiloxane with a specific structure in an addition-curable fluorosilicone composition that is liquid at 23°C, a fluorosilicone rubber that has good curing properties and retains mechanical strength can be obtained. Furthermore, they discovered that the liquid addition-curable fluorosilicone composition is suitable as a material for casting, compression molding, and injection molding, which led to the first aspect of the present invention. Specifically, the present invention provides the following fluorosilicone composition, fluorosilicone rubber, and molded article thereof.
- a first aspect of the present invention is an addition-curable fluorosilicone composition
- (A) a compound represented by the following general formula (1):
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group
- m is an integer from 0 to 100
- n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.
- a vinyl group-containing organopolysiloxane having a viscosity at 25° C.
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group.
- the fluorosilicone composition of the first aspect of the present invention contains, as a base, a linear polysiloxane whose main chain is a repeating structure of diorganosiloxane units having fluoroalkyl groups.
- a typical dimethylsilicone composition contains, as a base, a linear dimethylpolysiloxane whose main chain is a repeating structure of dimethylsiloxane units.
- the fluorosilicone composition of the first aspect of the present invention is essentially different from a dimethylsilicone composition.
- the present inventors have discovered that by using an alkenyl group-containing organopolysiloxane of a specific structure and a hydrogenpolysiloxane of a specific structure in an addition-curable fluorosilicone composition that is liquid at 23°C, a liquid addition-curable fluorosilicone composition can be obtained that can give a fluorosilicone rubber that has good curing properties and retains mechanical strength. Furthermore, they have discovered that this liquid addition-curable fluorosilicone composition is suitable as a material for injection molding, compression molding, and injection molding. Based on these findings, the present inventors have completed the second aspect of the present invention.
- the second aspect of the present invention is A liquid addition-curable fluorosilicone composition
- a liquid addition-curable fluorosilicone composition comprising: (A') a compound represented by the following general formula (1A):
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group
- m is an integer from 0 to 100
- n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.
- an alkenyl group-containing organopolysiloxane having a viscosity at 25° C.
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group.
- the second aspect of the present invention is a fluorosilicone rubber that is a cured product of the addition-curable fluorosilicone composition of the second aspect of the present invention.
- the addition-curable fluorosilicone composition of the first aspect of the present invention is characterized in that it contains (A) a specific vinyl-containing organopolysiloxane having a viscosity of 100 to 500,000 mPa ⁇ s at 25° C., (B) a specific branched organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms per molecule, (C) an addition reaction catalyst, and (D) a reinforcing silica filler that has been surface-treated with a specific organosilicon compound, and is in a liquid state at 23° C.
- the composition may further contain components other than the above components (A) to (D). These components will be described below.
- (A) Vinyl Group-Containing Organopolysiloxane Component (A) is an organopolysiloxane represented by the following general formula (1) and having a viscosity at 25° C. of 100 to 500,000 mPa ⁇ s.
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms;
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms;
- X is a divalent organic group;
- m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; k is an integer from 1 to 10; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.)
- R 1 may be, independently of one another, a group selected from an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, etc., an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, etc., and an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, etc.
- an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is particularly preferred.
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms.
- the perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10):
- the perfluoropolyether group is exemplified by the following formula: (s and t are integers from 1 to 9) Examples are given below.
- X is a divalent organic group.
- X functions as a spacer that connects the main chain of the linear vinyl group-containing organopolysiloxane of component (A) with the Rf group in the side chain, and can adjust the interaction between the Rf groups or between the Rf group and other molecules to make the properties of the cured product, such as the hydrocarbon solvent resistance, desirable.
- the divalent organic group is not particularly limited, but can be an alkylene group having 2 to 4 carbon atoms, some of the hydrogen atoms of which may be substituted with fluorine atoms or the like, and may have an oxygen atom, an ester bond, or an amide bond in the middle or at the end.
- this divalent organic group examples include those of the following formula: (* is a bond to the Rf group, and ** is a bond to the silicon atom)
- the Rf-X group is preferably a C k F 2k+1 -CH 2 CH 2 group (k is an integer of 1 to 10), and more preferably a 3,3,3-trifluoropropyl group (k is 1).
- n is an integer from 1 to 800, preferably from 5 to 750, more preferably from 10 to 650, even more preferably from 50 to 650, and most preferably from 100 to 650.
- (m+n) is an integer in the range of 5 ⁇ m+n ⁇ 800, preferably 10 ⁇ m+n ⁇ 680, more preferably 60 ⁇ m+n ⁇ 680, and even more preferably 120 ⁇ m+n ⁇ 680.
- the number of fluoroalkyl group-containing siloxane units is preferably 10 mol % or more, more preferably 20 mol % or more, and particularly preferably 30 to 100 mol %, of all siloxane units in the molecule (particularly the sum of the difunctional siloxane units constituting the main chain (i.e., n+m).
- the upper limit is not particularly limited as long as it is 100 mol % or less, and may be 95 mol % or less, 90 mol % or less, or 80 mol % or less. This range is preferable because it provides excellent hydrocarbon solvent resistance.
- the viscosity of the organopolysiloxane (A) is characterized by being in the range of 100 to 500,000 mPa ⁇ s at 25°C, and is preferably in the range of 300 to 100,000 mPa ⁇ s. Within this range, the physical properties of the cured product are good, and the handling and workability of the composition are good. Furthermore, if the viscosity is less than 100 mPa ⁇ s, the strength of the resulting cured product is insufficient, and if it exceeds 500,000 mPa ⁇ s, the handling of the composition decreases, which is not preferable. In the first embodiment of the present invention, the viscosity is a value measured with a rotational viscometer using the method described in JIS K 7117-1:1999. The degree of polymerization of the organopolysiloxane (A) is a value in which the viscosity at 25°C falls within the above range.
- Organohydrogenpolysiloxane Component (B) is a branched organohydrogenpolysiloxane represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in each molecule. This organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A) and acts as a curing agent (crosslinking agent).
- the molecular structure of component (B) is a branched siloxane modified with terminal hydrogen, and by including this organohydrogensiloxane, the fluorosilicone composition cures quickly, and the fluorosilicone rubber cured product can have high strength.
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms;
- Rf is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms; and
- X is a divalent organic group.
- x1 is a number of 2 ⁇ x1 ⁇ 4, x2 is an integer of 0 ⁇ x2 ⁇ 20, and x3 is an integer of 0 ⁇ x3 ⁇ 20, satisfying 0 ⁇ x2+x3 ⁇ 20; y1 is an integer of 0 ⁇ y1 ⁇ 30, z1 is an integer of 0 ⁇ z1 ⁇ 10, y2 is an integer of 0 ⁇ y2 ⁇ 30, z2 is an integer of 0 ⁇ z2 ⁇ 10, and z1+z2>0.)
- the monovalent organic group R4 bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and examples thereof include monovalent hydrocarbon groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, that do not contain an aliphatic unsaturated bond, such as an unsubstituted or substituted alkenyl group.
- Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups, and preferably a methyl group.
- alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decy
- the number of silicon atoms in one molecule of component (B) ((x1+x2+x3+y1+y2+z1+z2) or the degree of polymerization) is preferably 4 to 60, more preferably 4 to 50, and even more preferably 4 to 40.
- the monovalent organic group Rf bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms, and examples thereof include the groups shown for Rf in formula (1) above.
- a perfluoroalkyl group is preferred, and a trifluoromethyl group is more preferred.
- X is a divalent organic group, and examples thereof include the groups shown for X in formula (1) above.
- Rf-X group a C k F 2k+1 -CH 2 CH 2 group (k is an integer of 1 to 10) is preferable, and a 3,3,3-trifluoropropyl group (k is 1) is more preferable.
- x2, x3, y1, y2, z1, and z2 are not all 0 at the same time. Since z1+z2>0, the branched organohydrogenpolysiloxane represented by the above formula (3) contains one or more z1 units or z2 units, which are T units.
- component (B) examples include, but are not limited to, the branched organohydrogenpolysiloxanes shown below.
- Component (B) should be liquid at room temperature (25°C).
- the viscosity of component (B) at 25°C is preferably 0.1 to 1,000 mPa ⁇ s, more preferably 0.5 to 500 mPa ⁇ s, and even more preferably 1 to 200 mPa ⁇ s. A viscosity within this range will ensure good workability.
- the amount of component (B) is an amount such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.5 to 10 per silicon-bonded vinyl group in the composition.
- the ratio of the number of silicon-bonded hydrogen atoms (hydrosilyl groups) in component (B) to one silicon-bonded vinyl group (SiVi group) in the composition is within the range of 0.5 to 10, preferably 1 to 5. If the amount of component (B) is less than the lower limit, the resulting composition will not cure sufficiently. If the amount of component (B) exceeds the upper limit, the heat resistance of the resulting silicone rubber will be extremely poor.
- a vinyl-containing silicon compound such as a vinyl-containing organosiloxane other than component (A)
- component (B) it is sufficient that the ratio of the number of silicon-bonded hydrogen atoms in component (B) to the number of vinyl groups bonded to silicon atoms in the composition satisfies the above range.
- the component (B) may be used alone or in combination of two or more types.
- the branched organohydrogenpolysiloxane represented by formula (3) may contain hydroxyl groups and/or alkoxy groups in the molecule.
- hydroxyl groups and/or alkoxy groups having 1 to 6 carbon atoms may be contained within a range of 20 mol % or less of all the substituents of the organopolysiloxane.
- alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, t-butoxy groups, pentyloxy groups, neopentyloxy groups, and hexyloxy groups, and in particular methoxy groups, ethoxy groups, and isopropoxy groups.
- the addition reaction catalyst of the component (C) may be any catalyst that promotes the addition reaction between the vinyl group in the composition and the hydrogen atom bonded to the silicon atom in the component (B).
- platinum group metal catalysts are preferably used.
- the component (C) may be used alone or in combination of two or more.
- the amount of component (C) to be blended may be an effective amount as a catalyst (catalytic amount), but is usually in the range of 0.5 to 1,000 ppm, preferably 1 to 500 ppm, and more preferably 10 to 100 ppm, by mass, converted into catalytic metal element (platinum group metal element) relative to the amount of component (A). If this range is satisfied, the reaction rate of the addition reaction will be appropriate, and the heat resistance of the cured product will be good.
- Reinforcing Silica Filler Component (D) is a reinforcing silica that has been surface-treated with a linear organosilicon compound having silanol groups at both molecular chain terminals, as represented by the following formula (2).
- R 3 is, independently of each other, a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and examples thereof include those described above for R 1.
- a methyl group is preferable.
- R 2 is a group represented by R 3 above, or a 3,3,3-trifluoropropyl group, with the proviso that at least one R 2 is a 3,3,3-trifluoropropyl group.
- p is an integer satisfying 1 ⁇ p ⁇ 20, and is preferably an integer from 3 to 9.
- the reinforcing silica filler is essential for imparting mechanical strength to the resulting silicone rubber. If the organosilicon compound represented by the above formula (2) does not have a 3,3,3-trifluoropropyl group, the resulting cured product will have inferior tensile strength, elongation at break, compression set, etc.
- reinforcing silica filler that has been surface-treated with a linear organosilicon compound having both molecular chain terminals blocked with silanol groups, it is possible to reduce the viscosity of the composition and the compression set of the rubber after heat curing.
- the reinforcing silica filler those conventionally used in silicone rubber compositions can be used, and precipitated silica (wet silica), fumed silica (dry silica), fired silica, etc. are preferred. Fumed silica is particularly preferred.
- the (D) component is a surface-untreated silica that has been previously surface-treated with the organosilicon compound of formula (2).
- the surface-untreated silica may be kneaded with a polysiloxane component (i.e., component (A)), and the organosilicon compound of formula (2) may be added, and the mixture may be heated and mixed, preferably in the presence of a small amount of water, to perform surface treatment in the mixture.
- the surface-untreated silica used in the first aspect of the present invention refers to silica that has not been surface-treated with the organosilicon compound of formula (2), and may be dry silica (e.g., Aerosil R-974, etc.) that has been surface-treated with dimethyldichlorosilane or the like. It is preferable to further treat the surface of the dry silica that has been surface-treated with dimethyldichlorosilane or the like in this way with the organosilicon compound of formula (2).
- dry silica e.g., Aerosil R-974, etc.
- the amount of the organosilicon compound of formula (2) is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 40 parts by mass of silica before surface treatment with the organosilicon compound of formula (2).
- organosilanes and organosilazanes other than the organosilicon compound of formula (2) above may be used in combination as surface treatment agents.
- organosilanes include chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, and trivinylchlorosilane; alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, and vinyltris(methoxyethoxy)silane; and silazanes such as hexamethyldisilazane, hexamethylcyclo
- hexamethyldisilazane and 1,3-divinyl-1,1,3,3-tetramethyldisilazane are preferred.
- the amount of these organosilanes or organosilazanes used for surface treatment is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 40 parts by mass of untreated silica.
- the BET specific surface area of the silica before surface treatment with the organosilicon compound of formula (2) is 50 m 2 /g or more, preferably 100 to 400 m 2 /g, and more preferably 150 to 350 m 2 /g. If the specific surface area is 50 m 2 /g or more, sufficient strength is obtained and the appearance of the rubber molded product is also improved. If it is 400 m 2 /g or less, compounding is easy.
- the BET specific surface area of the silica after surface treatment may also be within the above range.
- the amount of component (D) to be blended is 10 to 60 parts by mass, and preferably 15 to 55 parts by mass, per 100 parts by mass of component (A). If the blending amount is less than the lower limit, the resulting silicone rubber will not have sufficient rubber strength, and if the blending amount exceeds the upper limit, it will be difficult to blend the silicone rubber into the composition.
- the liquid addition curable fluorosilicone composition of the first embodiment of the present invention may contain other components other than the components (A) to (D) as necessary.
- other components include conductive agents such as carbon black, conductive zinc oxide, and metal powder, nitrogen-containing compounds, acetylene compounds such as ethynylcyclohexanol, hydrosilylation reaction inhibitors such as phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds, heat resistance imparting agents such as iron oxide and cerium oxide, compression set improvers such as triazole compounds and benzotriazole derivatives such as benzotriazole silane, internal release agents such as dimethyl silicone oil, adhesion imparting agents, and thixotropy imparting agents.
- the liquid addition curable fluorosilicone composition of the first embodiment of the present invention does not contain an isocyanuric acid derivative having three trialkoxy groups in one molecule.
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention can be prepared by uniformly mixing the above components (A) to (D) and, if necessary, each optional component, using a conventional mixer, stirrer, kneader, or other such device as a kneader or planetary mixer.
- the composition of the first aspect of the present invention is characterized in that it is liquid at 23°C.
- liquid at 23°C means that it has a certain volume at 23°C, but changes shape (has fluidity) according to the shape of the container.
- the viscosity at 23°C and a shear rate of 10s -1 is preferably 1,500 Pa ⁇ s or less, more preferably 100 to 1,200 Pa ⁇ s, and even more preferably 200 to 1,100 Pa ⁇ s. If the viscosity exceeds 1,500 Pa ⁇ s, it may take a long time to supply the material when performing injection, compression, and injection molding, and productivity may be significantly reduced.
- the viscosity at the above shear rate was measured using a precision rotational viscometer (manufactured by Thermo Fisher Scientific).
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention can also be a two-liquid type.
- each component can be appropriately divided so that the crosslinking agent (B) and the addition reaction catalyst (C) are not mixed in the same composition (liquid A or B).
- a two-liquid type composition can be made consisting of liquid A containing components (A), (C), and (D), and liquid B containing components (A), (B), and (D), and it is preferable to prepare it so that they can be mixed in equal masses or volumes.
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention can be applied to various molding methods such as injection molding, compression molding, and injection molding. Below, the molding method of fluorosilicone rubber by injection molding, compression molding, or injection molding will be explained in detail.
- liquid addition-curing fluorosilicone composition is divided into two liquid types, liquid A and liquid B.
- the two liquids are mixed in equal amounts and injected into a metal mold, where they are heated and cured in a thermostatic bath to form silicone rubber.
- a metal mold is placed on a compressor such as a press, and equal amounts of the above liquids A and B are mixed in the same way as in injection molding, injected into the mold, where they are heated and cured to form silicone rubber.
- liquid A and liquid B are supplied from the material supply pump to a metering machine. From the metering machine, liquid A and liquid B are merged in equal amounts through the material supply line. The material is mixed in the screw and cylinder parts of the molding machine body. It is then injected into a mold, where it is heated and cured to form silicone rubber.
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention is particularly suitable for liquid silicone rubber injection molding systems (LIMS: Liquid Injection Molding System).
- LIMS is a molding processing system that combines liquid silicone rubber, which has excellent properties, with a molding machine that precisely and stably injects it, and can automate everything from mixing to molding, simplifying and shortening the process while facilitating the molding of high-quality products.
- the composition of the first aspect of the present invention has the following advantages: That is, (i) the curing speed is fast, and molding time can be shortened, which allows for shortening of the process; (ii) since the material is liquid, molding can be performed at low injection pressure, and precision parts can also be molded, improving productivity; (iii) since it is compatible with flash-free and runnerless molding and has excellent release properties after curing, the molding process can be automated; and (iv) since there are no by-products from the curing reaction, and since flash-free and runnerless molding eliminates the need for waste disposal, environmentally friendly manufacturing is possible.
- the first aspect of the present invention provides a fluorosilicone rubber that is a cured product of the above-mentioned addition-curable fluorosilicone composition.
- a fluorosilicone rubber can maintain good mechanical strength.
- the composition can be cured according to known techniques, and there are no particular limitations on the curing method or conditions.
- the conditions for hardening and molding (primary cure) of the liquid addition-curing fluorosilicone composition may be the same as those for known addition-reaction-curing silicone compositions, and the composition can be hardened and molded by heating at a hardening temperature of 80-220°C, particularly 120-200°C, and for a hardening time of 3 seconds to 10 minutes, particularly 5 seconds to 5 minutes. If necessary, the molded cured product may be post-cured (secondary cure), for example, at 180-220°C for about 30 minutes to 6 hours.
- the cured product (silicone rubber) obtained from the liquid addition-curable fluorosilicone composition of the present invention has a compression set of 10% or less after 22 hours of compression at 180°C, and a mechanical strength of tensile strength of 5.0 MPa or more, as measured according to the description of JIS K 6249:2003.
- the compression set of the cured product after 22 hours of compression at 180°C at a compression rate of 25%, as measured according to JIS K 6249:2003 should be 15% or less, preferably 10% or less.
- the cured product can be used as a part (molded product) such as a sealing material, O-ring, or packing.
- the mechanical strength should be tensile strength of 4.5 MPa or more, preferably 5.0 MPa or more.
- the first aspect of the present invention provides a fluorosilicone rubber molded article, which is a molded article of the above-mentioned fluorosilicone rubber.
- the fluorosilicone rubber molded products obtained by heat curing the liquid addition-curable fluorosilicone composition of the first aspect of the present invention have excellent gasoline and oil resistance, and are therefore suitable for use in aircraft and automotive rubber parts, printer parts, etc. In recent years, they have also been used in mobile parts due to their sebum resistance, and in sealing parts for fuel cell vehicles due to their acid resistance.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention generally comprises (A') an alkenyl-containing organopolysiloxane, (B') an organohydrogenpolysiloxane, (C') an addition reaction catalyst, and (D') a reinforcing silica filler.
- liquid addition-curable fluorosilicone composition according to the second aspect of the present invention are described in more detail below.
- Alkenyl Group-Containing Organopolysiloxane Component (A') is an alkenyl group (vinyl group)-containing organopolysiloxane represented by the following general formula (1A) and having a viscosity at 25°C of 100 to 500,000 mPa ⁇ s.
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms;
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms;
- X is a divalent organic group;
- m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.
- the component (A') is preferably represented by the following formula (1A'):
- R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; k is an integer from 1 to 10; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800.
- the organopolysiloxane has a perfluoroalkyl group and is represented by the formula:
- R 1 is, independently of each other, a group selected from alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group, aryl groups having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, and an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group.
- alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is particularly preferred.
- Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms.
- the perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10). Examples are given below.
- the perfluoropolyether group may be represented by the following formula: (s and t are each an integer from 1 to 9) Examples are given below.
- X is a divalent organic group.
- divalent organic group examples include those represented by the following formula: (* is a bond bonded to the Rf group, and ** is a bond bonded to the silicon atom)
- n is an integer from 1 to 800, preferably from 5 to 750, more preferably from 10 to 650, even more preferably from 50 to 650, and most preferably from 100 to 650.
- (m+n) is an integer in the range of 5 ⁇ m+n ⁇ 800, preferably 10 ⁇ m+n ⁇ 680, more preferably 60 ⁇ m+n ⁇ 680, and even more preferably 120 ⁇ m+n ⁇ 680.
- the viscosity of the organopolysiloxane of component (A') is characterized by being in the range of 100 to 500,000 mPa ⁇ s at 25°C, and is preferably in the range of 300 to 100,000 mPa ⁇ s. Within this range, the physical properties of the cured product are good, and the handling and workability of the composition are good. Furthermore, if the viscosity is less than 100 mPa ⁇ s, the strength of the resulting cured product is insufficient, and if it exceeds 500,000 mPa ⁇ s, the handling of the composition is reduced, which is not preferable.
- the viscosity is a value measured with a rotational viscometer using the method described in JIS K 7117-1:1999.
- the degree of polymerization of organopolysiloxane (A') is a value in which the viscosity at 25°C falls within the above range.
- the number of siloxane units having a perfluoroalkyl group or a perfluoropolyether group is preferably 10 mol % or more, more preferably 20 mol % or more, and particularly preferably 30 to 100 mol %, of all siloxane units in the molecule (particularly the sum of the bifunctional siloxane units constituting the main chain (i.e., n + m).
- the upper limit is not particularly limited as long as it is 100 mol % or less, and may be 95 mol % or less, 90 mol % or less, or 80 mol % or less. This range is preferable because it can provide excellent hydrocarbon solvent resistance.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention contains as a base a linear polysiloxane whose main chain is a repeating structure of diorganosiloxane units having perfluoroalkyl groups or perfluoropolyether groups.
- a typical dimethylsilicone composition contains as a base a linear dimethylpolysiloxane whose main chain is a repeating structure of dimethylsiloxane units.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention is essentially different from a dimethylsilicone composition.
- the organohydrogenpolysiloxane of the component (B') is represented by the following formula (2A):
- R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms
- X is a divalent organic group.
- the organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
- the organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A') and acts as a curing agent (crosslinking agent).
- component (B') is preferably a branched siloxane modified with terminal hydrogen, and by including this organohydrogensiloxane, the silicone rubber cured product can be cured quickly and with high strength.
- the organohydrogenpolysiloxane of component (B') is preferably represented by the following formula (2A'):
- R4 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- X is a divalent organic group.
- x1' is an integer of 3 ⁇ x1' ⁇ 5, x2' and x3' are integers of 0 ⁇ x2'+x3' ⁇ 20, y1' is an integer of 0 ⁇ y1' ⁇ 30, y2' is an integer of 0 ⁇ y2' ⁇ 30, w is 0 ⁇ w ⁇ 10, and k is an integer of 1 to 10, with the proviso that x2', x3', y1', and y2' are not all 0 at the same time.)
- the organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
- Examples of monovalent organic groups R4 bonded to silicon atoms other than hydrogen atoms bonded to silicon atoms include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which are unsubstituted or substituted monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, such as alkenyl groups, aryl groups having 6 to 12 carbon atoms that do not contain aliphatic unsaturated bonds, and aralkyl groups having 7 to 12 carbon atoms that do not contain aliphatic unsaturated bonds.
- Examples of such groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, cyclohexyl groups, octyl groups, nonyl groups, and decyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups, and aralkyl groups such as benzyl groups, phenylethyl groups, and phenylpropyl groups, with methyl groups being preferred.
- alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups,
- the number of silicon atoms (or degree of polymerization) in one molecule of component (B') is preferably 4 to 60, more preferably 4 to 50, and even more preferably 4 to 40.
- the monovalent organic group Rf' bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoropolyether group having 3 to 30 carbon atoms, preferably a perfluoroalkyl group, and more preferably a 3,3,3-trifluoropropyl group.
- Component (B') should be liquid at room temperature (25°C).
- the viscosity of component (B') at 25°C is preferably 0.1 to 1,000 mPa ⁇ s, more preferably 0.5 to 500 mPa ⁇ s, and even more preferably 1 to 200 mPa ⁇ s. If the viscosity at 25°C is 0.1 to 1,000 mPa ⁇ s, good workability can be achieved.
- the amount of component (B') is such that the ratio of the number of silicon-bonded hydrogen atoms in component (B') to one silicon-bonded alkenyl group in the composition of the second embodiment of the present invention is within the range of 0.5 to 10, preferably 1 to 5. If the amount of component (B') is less than the above lower limit, the resulting composition will not cure sufficiently. If the amount of component (B') exceeds the above upper limit, the heat resistance of the resulting silicone rubber will be extremely poor.
- component (A') when an alkenyl-containing organosiloxane other than component (A') described below is included, it is sufficient that the ratio of the number of silicon-bonded hydrogen atoms in component (B') to the number of alkenyl groups bonded to silicon atoms in the composition satisfies the above range.
- the (B') component may be used alone or in combination of two or more types.
- the (B') component may be used in combination with two or more types of organohydrogenpolysiloxanes having two or more silicon-bonded hydrogen atoms in each molecule.
- the addition reaction catalyst of component (C') may be any catalyst that promotes the addition reaction between the alkenyl group (vinyl group) in component (A') and the hydrogen atom bonded to the silicon atom in component (B'). Usually, platinum group metal catalysts are preferably used.
- platinum, palladium, rhodium, etc. chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxane or acetylene compounds, tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., platinum group metals or compounds thereof are listed, and particularly preferred are platinum compounds.
- Component (C') may be used alone or in combination of two or more types.
- the amount of component (C') to be blended may be an effective amount as a catalyst, but is usually in the range of 0.5 to 1,000 ppm, preferably 1 to 500 ppm, and more preferably 10 to 100 ppm, by mass, converted into catalytic metal element (platinum group metal element) relative to the amount of component (A'). If this range is satisfied, the reaction rate of the addition reaction will be appropriate, and the heat resistance of the cured product will be good.
- (D') Reinforcing Silica Filler Component (D') is a reinforcing silica that has been surface-treated with a linear organosilicon compound having silanol groups at both molecular chain terminals, represented by the following formula (3A).
- R 3 is, independently of each other, a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and examples thereof include those described above for R 1.
- a methyl group is preferable.
- R 2 is, independently of each other, a group represented by R 3 above, or a 3,3,3-trifluoropropyl group, with the proviso that at least one of R 2 is a 3,3,3-trifluoropropyl group.
- p is an integer satisfying 1 ⁇ p ⁇ 20, and is preferably an integer from 3 to 9.
- the reinforcing silica filler is essential for imparting mechanical strength to the resulting silicone rubber. If the organosilicon compound represented by the above formula (3A) does not have a 3,3,3-trifluoropropyl group, the resulting cured product will have inferior tensile strength, elongation at break, compression set, etc.
- the reinforcing silica filler may be any of those conventionally used in silicone rubber compositions, with precipitated silica (wet silica), fumed silica (dry silica), calcined silica, etc. being preferred. Fumed silica is particularly preferred.
- the (D') component may be surface-untreated silica that has been previously surface-treated with the organosilicon compound of formula (3A).
- the surface-untreated silica may be kneaded with a polysiloxane component (i.e., component (A')), and the organosilicon compound of formula (3A) may be added, and the mixture may be heated and mixed, preferably in the presence of a small amount of water, to perform surface treatment in the mixture.
- the surface-untreated silica used in the second aspect of the present invention may preferably be dry silica (e.g., Aerosil R-974, etc.) that has been surface-treated with dimethyldichlorosilane or the like. It is preferable to further treat the surface of the dry silica that has been surface-treated with dimethyldichlorosilane or the like in this way with the organosilicon compound of formula (3A).
- the amount of the organosilicon compound of formula (3A) is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 40 parts by mass of silica prior to surface treatment with the organosilicon compound of formula (3A).
- organosilanes and organosilazanes other than the organosilicon compound of the above formula (3A) may be used in combination as a surface treatment agent.
- organosilanes include chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, and trivinylchlorosilane, alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, and vinyltris(methoxyethoxy)silane, and silazanes such as hexamethyldisilazane, he
- the BET specific surface area of the silica before surface treatment with the organosilicon compound of formula (3A) is 50 m 2 /g or more, preferably 100 to 400 m 2 /g, and more preferably 150 to 350 m 2 /g. If the specific surface area is 50 m 2 /g or more, sufficient strength is obtained and the appearance of the rubber molded product is good. If the specific surface area is 400 m 2 /g or less, compounding is easy.
- the BET specific surface area of the silica after surface treatment may also be within the above range.
- the amount of component (D') is 10 to 60 parts by mass, and preferably 15 to 55 parts by mass, per 100 parts by mass of component (A'). If the amount is less than the lower limit, the resulting silicone rubber will not have sufficient rubber strength, and if the amount is more than the upper limit, it will be difficult to incorporate it into the composition.
- the liquid addition-curable fluorosilicone composition according to the second embodiment of the present invention may contain other components in addition to the above-mentioned components (A') to (D'), as necessary. There are no particular limitations on the amounts added.
- conductive agents such as carbon black, conductive zinc oxide, and metal powder
- hydrosilylation reaction inhibitors such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds
- heat resistance imparting agents such as iron oxide and cerium oxide
- compression set improvers such as triazole compounds and benzotriazole derivatives
- internal release agents such as dimethyl silicone oil
- adhesive agents and thixotropy imparting agents.
- thixotropy imparting agents It is preferable that the liquid addition-curable fluorosilicone composition of the second aspect of the present invention does not contain an isocyanuric acid derivative having three trialkoxy groups in one molecule.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention can be prepared, for example, by uniformly mixing the above-mentioned components (A') to (D'), and, if necessary, each optional component, using a conventional mixer/stirrer, kneader, or other such device as a kneader or planetary mixer.
- the composition according to the second aspect of the present invention is characterized in that it is liquid at 23°C.
- the viscosity at 23°C and a shear rate of 10s -1 is preferably 1,500 Pa ⁇ s or less, more preferably 100 to 1,200 Pa ⁇ s, and even more preferably 200 to 1,100 Pa ⁇ s. If the viscosity is 1,500 Pa ⁇ s or less, it does not take much time to supply the material when performing injection, compression, and injection molding, and high productivity can be provided.
- the viscosity at the above shear rate was measured using a precision rotational viscometer (manufactured by Thermo Fisher Scientific).
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention can also be a two-liquid type.
- each component can be appropriately divided so that the crosslinking agent (B') and the addition reaction catalyst (C') are not mixed in the same composition (Liquid A or Liquid B).
- a two-liquid type composition can be made consisting of Liquid A containing components (A'), (C'), and (D') and Liquid B containing components (A'), (B'), and (D'), and it is preferable to prepare it so that it can be mixed in equal masses or volumes.
- the fluorosilicone rubber is a cured product of the addition-curable fluorosilicone composition according to the second aspect of the present invention.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention can be applied to various molding methods such as injection molding, compression molding, and injection molding.
- injection molding compression molding
- injection molding injection molding
- injection molding compression molding
- injection molding injection molding
- liquid addition-curing fluorosilicone composition is divided into two liquids, liquid A and liquid B.
- the two liquid materials (components) are mixed in equal amounts and injected into a metal mold, where they are heated in a thermostatic bath to harden and form silicone rubber.
- a metal mold is placed on a compressor such as a press, and equal amounts of the above liquids A and B are mixed in the same way as in injection molding, and then injected into the mold, where it is heated to harden and form the silicone rubber.
- liquid A and liquid B are supplied to a metering machine from a material supply pump. From the metering machine, liquid A and liquid B join together in equal amounts through a material supply line. The materials are mixed in the screw and cylinder sections of the molding machine body. They are then injected into a mold, where they are heated and hardened to form silicone rubber.
- the conditions for hardening and molding (primary cure) of the liquid addition-curing fluorosilicone composition may be the same as those for known addition-reaction-curing silicone compositions, and the composition can be hardened and molded by heating at a hardening temperature of 80-220°C, particularly 120-200°C, and for a hardening time of 3 seconds to 10 minutes, particularly 5 seconds to 5 minutes. If necessary, the molded cured product may be post-cured (secondary cure), for example, at 180-220°C for about 30 minutes to 6 hours.
- the cured product (silicone rubber) obtained from the liquid addition-curable fluorosilicone composition of the second aspect of the present invention may have a compression set of 10% or less after 22 hours of compression at 180°C, as measured according to the description of JIS K 6249:2003, and a tensile strength of 5.0 MPa or more as mechanical strength.
- the compression set of the cured product may be 15% or less, and preferably 10% or less, as measured according to JIS K 6249:2003, after 22 hours of compression at 180°C with a compression ratio of 25%.
- the cured product can be used as a part (molded body) such as a sealing material, O-ring, or packing.
- the mechanical strength is preferably 4.5 MPa or more in tensile strength, and more preferably 5.0 MPa or more.
- the fluorosilicone rubber molded product (silicone rubber) obtained by heat curing the liquid addition-curable fluorosilicone composition of the second aspect of the present invention has excellent gasoline and oil resistance, and can therefore be suitably used for aircraft and automotive rubber parts, printer parts, etc. In recent years, it has also been suitable for use in mobile parts due to its sebum resistance, and sealing parts for fuel cell vehicles due to its acid resistance.
- the curability of the composition was measured using a curability tester [rotorless disc rheometer, moving die rheometer, or MDR] at 130°C for 3 minutes, with the 10% and 90% curing times (i.e., the time from the start of measurement at 130°C to give 10% and 90% torque values of the maximum torque value in 3 minutes from the start of measurement) defined as T10 and T90 (seconds).
- the hardness, tensile strength, elongation at break, and tear strength (angle) of the cured product were measured by the following methods.
- the composition was press-cured at 150° C. for 10 minutes and then post-cured in a thermostatic chamber at 200° C. for 4 hours.
- the hardness (type A durometer hardness), tensile strength, elongation at break, and tear strength (angle) of the resulting cured product were measured according to the specifications of JIS K 6249:2003.
- the compression set of the cured product was measured by the following method.
- the composition was cured (press cured) at 150° C. for 15 minutes, and then secondary vulcanized (post cured) in a thermostatic chamber at 200° C. for 4 hours.
- the compression set of the resulting cured product was measured after compression at 180° C. for 22 hours at a compression ratio of 25% according to the description of JIS K 6249:2003.
- Example 1 to 4 and Comparative Examples 1 and 2 The components used in the following Examples 1 to 4 and Comparative Examples 1 and 2 are as follows.
- Component (D) fumed silica having a specific surface area of 200 m 2 /g as measured by the BET method (Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.); An organosilicon compound represented by the following formula (5):
- Reaction inhibitor ethynylcyclohexanol
- Compression set improver benzotriazole silane represented by the following formula (7)
- Heat resistance agent cerium oxide
- silicone rubber base A1 60 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4) was added, and after mixing for 30 minutes, silicone rubber base A1 was obtained.
- the amount of component (D) per 100 parts by mass of component (A) was 35 parts by mass.
- Examples 1 to 4 A silicone rubber composition was prepared in the amounts shown in Table 1 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the above general physical properties were measured. These results are shown in Table 1.
- the "Curability T10/T90” column shows the 10% and 90% curing times (seconds) determined by the above measurement method, and the “Curability T90-T10” column shows the difference between them. The smaller the difference, the faster the curing.
- SiH/SiVi is the ratio of the number of SiH groups in component (B) to the number of SiVi groups in the composition.
- the cured product obtained from the liquid addition-curable fluorosilicone composition of the first embodiment of the present invention has good curability (fast curing) and excellent tensile strength and elongation at break.
- the fluorosilicone compositions of Comparative Examples 1 and 2, which use linear silicone (B-4) whose side chains are hydrogen-modified with the organosilicon compound according to the first embodiment of the present invention have poor curability (slightly slow curing) and also have poor mechanical strength.
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention is suitable as a material for casting, compression molding, and injection molding, and can contribute to improving the productivity of molded products.
- the liquid addition-curable fluorosilicone composition of the first aspect of the present invention has a low compression set value after heat curing, and can be suitably used as rubber molded products such as sealing materials, O-rings, and packings.
- Example 5 to 8 and Comparative Example 3 the storage stability of the compositions was evaluated by the following method. After storing the composition at 30° C. for 3 days or 7 days, the composition was visually inspected to determine whether it maintained fluidity and was liquid, and whether it had gelled, and was evaluated as "good.”
- Component (A') Formula (4') below Trifluoropropylmethylpolysiloxane having a viscosity of 76.6 Pa ⁇ s at 25° C. and both ends capped with dimethylvinylsiloxy groups [vinyl group content: 4.6 ⁇ 10 ⁇ 5 mol/g]
- (B') Crosslinking agent: (B'-1) Methylhydrogenpolysiloxane represented by the following formula (6-1') [SiH group amount: 0.012 mol/g]
- Reaction inhibitor ethynylcyclohexanol
- Compression set improver benzotriazole silane represented by the following formula (7)
- Heat resistance agent cerium oxide
- Examples 5 to 8 and Comparative Example 3 A silicone rubber composition was prepared in the amounts shown in Table 2 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the general physical properties described above were measured. The results are shown in Table 2.
- liquid addition-curable fluorosilicone compositions of Examples 5 to 7, which are examples of the second aspect of the present invention cure much faster than the compositions of Comparative Example 3 and Example 8, and the cured products of these compositions have better tensile strength and elongation at break than the cured products of the compositions of Comparative Example 3 and Example 8.
- the fluorosilicone composition of Comparative Example 3 which uses a silicone whose side chains are hydrogen-modified with an organosilicon compound of the second aspect of the present invention and does not contain SiO 4/2 units, cures somewhat slowly, and the cured products of these compositions also have inferior mechanical strength.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention is suitable as a material for casting, compression molding, and injection molding, and can contribute to improving the productivity of molded products.
- the liquid addition-curable fluorosilicone composition of the second aspect of the present invention has a low compression set value after heat curing, and can be suitably used as rubber molded products such as sealing materials, O-rings, and packings.
- the present invention is not limited to the above-described embodiments.
- the above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and provides similar effects is included within the technical scope of the present invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A first aspect of the present invention is a liquid addition-curable fluorosilicone composition characterized by comprising: (A) a vinyl group-containing organopolysiloxane represented by general formula (1) and having a viscosity at 25ºC of 100-500,000 mPa·s; (B) a branched organohydrogen polysiloxane represented by formula (3) and having three or more silicon atom-bonded hydrogen atoms per molecule, the content of the component (B) being such that the number of hydrogen atoms bonded to silicon atoms in the component (B) is 0.5-10 per silicon atom-bonded vinyl group in the composition; (C) an addition reaction catalyst at a catalytic amount; and (D) a reinforcing silica filler that has been surface treated with an organosilicon compound represented by general formula (2), the content of the reinforcing silica filler being 10-60 parts by mass per 100 parts by mass of the component (A), and the composition being a liquid at 23ºC. Through this, a liquid addition-curable fluorosilicone composition that exhibits excellent curability, maintains mechanical strength, and is suitable for injection molding and the like can be provided.
Description
本発明は、液状付加硬化型フルオロシリコーン組成物及び該組成物を加熱硬化して得られるフルオロシリコーンゴム及びその成形品に関するものである。
The present invention relates to a liquid addition-curable fluorosilicone composition, a fluorosilicone rubber obtained by heat-curing the composition, and a molded article thereof.
従来、付加硬化型フルオロシリコーンゴム組成物は、その硬化物が耐ガソリン性や耐油性に優れるため、航空機や車載用ゴム部品、プリンター部品等に使用されてきた（特許文献１）。また、近年、付加硬化型フルオロシリコーンゴム組成物の硬化物は、皮脂耐性の点からモバイル部品に、耐酸性の点から燃料電池車用シール部品における使用が検討されている。これらの部品に用いる付加硬化型フルオロシリコーンゴム組成物の硬化物は、圧縮永久ひずみが低く、実用強度すなわち機械的強度が保持されていることが求められている。特に、生産性に優れる液状付加硬化型フルオロシリコーンゴム組成物の開発が望まれていた。生産性に優れる加工方法としては、金型を使用する、注入成形、圧縮成形及び射出成形等が良いが、液状付加硬化型フルオロシリコーンゴム組成物は、それらの加工方法で適用できる粘度でないと使用できない問題点があった。
Conventionally, addition-cured fluorosilicone rubber compositions have been used in aircraft and vehicle rubber parts, printer parts, etc., because the cured products have excellent gasoline and oil resistance (Patent Document 1). In recent years, the use of cured products of addition-cured fluorosilicone rubber compositions in mobile parts from the viewpoint of sebum resistance, and in sealing parts for fuel cell vehicles from the viewpoint of acid resistance, has been considered. The cured products of addition-cured fluorosilicone rubber compositions used in these parts are required to have low compression set and to maintain practical strength, i.e., mechanical strength. In particular, the development of a liquid addition-cured fluorosilicone rubber composition with excellent productivity has been desired. Examples of processing methods with excellent productivity include injection molding, compression molding, and injection molding using a mold, but there is a problem that liquid addition-cured fluorosilicone rubber compositions cannot be used unless they have a viscosity that can be applied to these processing methods.
本発明の第１態様は、上記事情に鑑みなされたもので、硬化性が良好で、機械的強度が保持され、射出成形などに好適な液状付加硬化型フルオロシリコーン組成物を提供することを目的とする。また、前記組成物を加熱硬化して得られるフルオロシリコーンゴム及びその成形品を提供することも目的とする。
The first aspect of the present invention has been made in consideration of the above circumstances, and aims to provide a liquid addition-curable fluorosilicone composition that has good curability, retains mechanical strength, and is suitable for injection molding and the like. It also aims to provide a fluorosilicone rubber and a molded article thereof obtained by heat-curing the composition.
また、本発明の第２態様は、上記事情に鑑みなされたもので、硬化性が非常に良好でありながら保存安定性にも優れ、機械的強度が保持されるフルオロシリコーンゴムを与えることができ、生産性に優れた加工に好適な液状付加硬化型フルオロシリコーン組成物を提供することを目的とする。また、前記組成物を硬化して得られるフルオロシリコーンゴムを提供することも目的とする。
The second aspect of the present invention has been made in consideration of the above circumstances, and aims to provide a liquid addition-curable fluorosilicone composition that has very good curability, excellent storage stability, and can give a fluorosilicone rubber that retains mechanical strength, and is suitable for processing with excellent productivity. It also aims to provide a fluorosilicone rubber obtained by curing the composition.
上記課題を解決するために、本発明の第１態様では、付加硬化型フルオロシリコーン組成物であって、（Ａ）下記一般式（１）
（式中、Ｒ１は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である。）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、
（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）
（上記式（３）中、Ｒ４は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１は２≦ｘ１≦４の数、ｘ２は０≦ｘ２≦２０の整数、ｘ３は０≦ｘ３≦２０の整数であり、０≦ｘ２＋ｘ３≦２０を満たし、ｙ１は０≦ｙ１≦３０の整数、ｚ１は０≦ｚ１≦１０の整数、ｙ２は０≦ｙ２≦３０の整数であり、ｚ２は０≦ｚ２≦１０の整数であり、ｚ１＋ｚ２＞０である。）
で示される分岐状オルガノハイドロジェンポリシロキサン：（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量、
（Ｃ）付加反応触媒：触媒量、及び
（Ｄ）下記一般式（２）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
（上記式（２）中、Ｒ３は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、Ｒ２は互いに独立に、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基であり、ｐは１≦ｐ≦２０の整数である。）：（Ａ）成分１００質量部に対し１０～６０質量部
を含有し、
前記付加硬化型フルオロシリコーン組成物が２３℃で液状であることを特徴とする付加硬化型フルオロシリコーン組成物を提供する。 In order to solve the above problems, a first aspect of the present invention provides an addition-curable fluorosilicone composition, comprising: (A) a fluorosilicone compound represented by the following general formula (1):
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
a vinyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B) a compound represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in one molecule:
(In the above formula (3), R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms; and X is a divalent organic group. x1 is a number of 2≦x1≦4, x2 is an integer of 0≦x2≦20, and x3 is an integer of 0≦x3≦20, satisfying 0≦x2+x3≦20; y1 is an integer of 0≦y1≦30, z1 is an integer of 0≦z1≦10, y2 is an integer of 0≦y2≦30, z2 is an integer of 0≦z2≦10, and z1+z2>0.)
a branched organohydrogenpolysiloxane represented by the formula:
(C) an addition reaction catalyst: a catalytic amount; and (D) a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (2):
(In the above formula (2), R 3 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R 2 's are each independently a group represented by the above R 3 or a 3,3,3-trifluoropropyl group, with the proviso that at least one R 2 is a 3,3,3-trifluoropropyl group, and p is an integer satisfying 1≦p≦20.): the compound contains 10 to 60 parts by mass per 100 parts by mass of component (A),
The addition-curable fluorosilicone composition is characterized in that it is liquid at 23°C.
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、
（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）
で示される分岐状オルガノハイドロジェンポリシロキサン：（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量、
（Ｃ）付加反応触媒：触媒量、及び
（Ｄ）下記一般式（２）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有し、
前記付加硬化型フルオロシリコーン組成物が２３℃で液状であることを特徴とする付加硬化型フルオロシリコーン組成物を提供する。 In order to solve the above problems, a first aspect of the present invention provides an addition-curable fluorosilicone composition, comprising: (A) a fluorosilicone compound represented by the following general formula (1):
a vinyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B) a compound represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in one molecule:
a branched organohydrogenpolysiloxane represented by the formula:
(C) an addition reaction catalyst: a catalytic amount; and (D) a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (2):
The addition-curable fluorosilicone composition is characterized in that it is liquid at 23°C.
本発明の第１態様の付加硬化型フルオロシリコーン組成物であれば、硬化性が良好で、機械的強度が保持され、射出成形などに好適である。
The addition-curable fluorosilicone composition of the first aspect of the present invention has good curability, maintains mechanical strength, and is suitable for injection molding, etc.
また、本発明の第１態様は上記付加硬化型フルオロシリコーン組成物の硬化物であることを特徴とするフルオロシリコーンゴムを提供する。
The first aspect of the present invention provides a fluorosilicone rubber that is a cured product of the above-mentioned addition-curable fluorosilicone composition.
本発明の第１態様のフルオロシリコーンゴムであれば、良好な機械的強度を保持している。
The fluorosilicone rubber of the first aspect of the present invention maintains good mechanical strength.
また、本発明の第１態様は上記フルオロシリコーンゴムの成形体であることを特徴とするフルオロシリコーンゴム成形品を提供する。
The first aspect of the present invention provides a fluorosilicone rubber molded article, which is a molded article of the above-mentioned fluorosilicone rubber.
本発明の第１態様のフルオロシリコーンゴム成形品は、耐ガソリン性、耐油性に優れることから、航空機や車載用ゴム部品、プリンター部品等に好適に用いることができ、皮脂耐性の点からモバイル部品に、耐酸性の点から燃料電池車用シール部品にも好適に用いることができる。
The fluorosilicone rubber molded product of the first aspect of the present invention has excellent gasoline and oil resistance, making it suitable for use in aircraft and automotive rubber parts, printer parts, etc. Its sebum resistance makes it suitable for use in mobile parts, and its acid resistance makes it suitable for use in sealing parts for fuel cell vehicles.
また、上記課題を解決するために、本発明の第２態様では、
液状付加硬化型フルオロシリコーン組成物であって、
（Ａ’）下記一般式（１Ａ）
（式中、Ｒ１は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは、互いに独立に、炭素数１～１０のパーフルオロアルキル基、又は３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基含有オルガノポリシロキサン、
（Ｂ’）下記一般式（２Ａ）
（上記式（２Ａ）中、Ｒ４は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆ’は、互いに独立に、炭素数１～１０のパーフルオロアルキル基、または３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１’は３≦ｘ１’≦５の整数であり、ｘ２’及びｘ３’は０≦ｘ２’＋ｘ３’≦２０の整数であり、ｙ１’は０≦ｙ１’≦３０の整数であり、ｙ２’は０≦ｙ２’≦３０の整数であり、ｚ１’は０≦ｚ１’≦１０の整数であり、ｚ２’は０≦ｚ２’≦１０の整数であり、ｗは０＜ｗ≦１０であり、ただし、ｘ２’、ｘ３’、ｙ１’、ｙ２’、ｚ１’及びｚ２’は同時に０とならない。）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサン：（Ｂ’）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合アルケニル基１個当たり０．５～１０となる量、
（Ｃ’）付加反応触媒：触媒量、及び
（Ｄ’）下記一般式（３Ａ）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
（上記式（３Ａ）中、Ｒ３は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、Ｒ２は、互いに独立に、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基であり、ｐは１≦ｐ≦２０の整数である）：（Ａ’）成分１００質量部に対し１０～６０質量部
を含有するものであることを特徴とする、２３℃で液状である、付加硬化型フルオロシリコーン組成物を提供する。 In order to solve the above problem, in a second aspect of the present invention,
A liquid addition-curable fluorosilicone composition comprising:
(A') a compound represented by the following general formula (1A):
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
an alkenyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B') a compound represented by the following general formula (2A):
(In the above formula (2A), R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; and X is a divalent organic group. x1' is an integer of 3≦x1'≦5;x2' and x3' are integers of 0≦x2'+x3'≦20;y1' is an integer of 0≦y1'≦30;y2' is an integer of 0≦y2'≦30;z1' is an integer of 0≦z1'≦10;z2' is an integer of 0≦z2'≦10; and w is 0<w≦10, with the proviso that x2', x3', y1', y2', z1', and z2' are not simultaneously 0.)
an organohydrogenpolysiloxane having 3 to 5 silicon-bonded hydrogen atoms per molecule, represented by the formula:
(C') an addition reaction catalyst: a catalytic amount; and (D') a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (3A):
(In the above formula (3A), each R3 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and each R2 is independently a group represented by the above R3 or a 3,3,3-trifluoropropyl group, with the proviso that at least one R2 is a 3,3,3-trifluoropropyl group and p is an integer satisfying 1≦p≦20): An addition-curable fluorosilicone composition which is liquid at 23°C and contains 10 to 60 parts by mass of component (A') per 100 parts by mass of component (A') is provided.
液状付加硬化型フルオロシリコーン組成物であって、
（Ａ’）下記一般式（１Ａ）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基含有オルガノポリシロキサン、
（Ｂ’）下記一般式（２Ａ）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサン：（Ｂ’）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合アルケニル基１個当たり０．５～１０となる量、
（Ｃ’）付加反応触媒：触媒量、及び
（Ｄ’）下記一般式（３Ａ）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有するものであることを特徴とする、２３℃で液状である、付加硬化型フルオロシリコーン組成物を提供する。 In order to solve the above problem, in a second aspect of the present invention,
A liquid addition-curable fluorosilicone composition comprising:
(A') a compound represented by the following general formula (1A):
an alkenyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B') a compound represented by the following general formula (2A):
an organohydrogenpolysiloxane having 3 to 5 silicon-bonded hydrogen atoms per molecule, represented by the formula:
(C') an addition reaction catalyst: a catalytic amount; and (D') a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (3A):
このような本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、比較的低温でも速やかに硬化するため硬化性が非常に良好でありながら保存安定性にも優れ、硬化により、機械的強度が保持されるフルオロシリコーンゴムを与えることができる。この液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形などの生産性に優れた加工用の材料として好適であることから、成形品の生産性向上に寄与することができる。
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention cures quickly even at relatively low temperatures, and therefore has very good curing properties while also having excellent storage stability, and can give a fluorosilicone rubber that retains its mechanical strength upon curing. This liquid addition-curable fluorosilicone composition is suitable as a material for highly productive processing such as casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
また、本発明の第２態様は、本発明の第２態様の付加硬化型フルオロシリコーン組成物の硬化物であることを特徴とするフルオロシリコーンゴムを提供する。
The second aspect of the present invention provides a fluorosilicone rubber that is a cured product of the addition-curable fluorosilicone composition of the second aspect of the present invention.
本発明の第２態様のフルオロシリコーンゴムは、低い圧縮永久ひずみ及び高い機械的強度を示すことができる。
The fluorosilicone rubber of the second aspect of the present invention can exhibit low compression set and high mechanical strength.
本発明の第１態様の付加硬化型フルオロシリコーン組成物は、液状で、比較的低温でも速やかに硬化するため硬化性が良好であり、機械的強度が保持されるフルオロシリコーンゴムを与える。また、この液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形用材料として好適であることから、成形品の生産性向上に寄与することができる。
The addition-curable fluorosilicone composition of the first aspect of the present invention is liquid and cures quickly even at relatively low temperatures, resulting in good curing properties and a fluorosilicone rubber that retains its mechanical strength. Furthermore, this liquid addition-curable fluorosilicone composition is suitable as a material for casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
また、以上のように、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、比較的低温でも速やかに硬化するため硬化性が非常に良好でありながら保存安定性にも優れ、機械的強度が保持されるフルオロシリコーンゴムを与えることができる。また、この液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形などの生産性に優れた加工用の材料として好適であることから、成形品の生産性向上に寄与することができる。
As described above, the liquid addition-curable fluorosilicone composition of the second aspect of the present invention cures quickly even at relatively low temperatures, and therefore has very good curing properties while also having excellent storage stability, making it possible to give a fluorosilicone rubber that retains its mechanical strength. Furthermore, this liquid addition-curable fluorosilicone composition is suitable as a material for highly productive processing such as casting, compression molding, and injection molding, and can therefore contribute to improving the productivity of molded products.
また、本発明の第２態様のフルオロシリコーンゴムは、低い圧縮永久ひずみ及び高い機械的強度を示すことができる。
Furthermore, the fluorosilicone rubber of the second aspect of the present invention can exhibit low compression set and high mechanical strength.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、２３℃で液状である付加硬化型フルオロシリコーン組成物に、特定構造のハイドロジェンポリシロキサンを用いることで、硬化性が良好で機械的強度が保持されるフルオロシリコーンゴムが得られることを見出した。さらに、該液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形用材料として好適であることを見出し、本発明の第１態様をなすに至ったものである。具体的には、以下のようなフルオロシリコーン組成物、フルオロシリコーンゴム及びその成形品を提供するものである。
The inventors conducted extensive research to achieve the above object, and discovered that by using a hydrogen polysiloxane with a specific structure in an addition-curable fluorosilicone composition that is liquid at 23°C, a fluorosilicone rubber that has good curing properties and retains mechanical strength can be obtained. Furthermore, they discovered that the liquid addition-curable fluorosilicone composition is suitable as a material for casting, compression molding, and injection molding, which led to the first aspect of the present invention. Specifically, the present invention provides the following fluorosilicone composition, fluorosilicone rubber, and molded article thereof.
即ち、本発明の第１態様は、付加硬化型フルオロシリコーン組成物であって、
（Ａ）下記一般式（１）
（式中、Ｒ１は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である。）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、
（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）
（上記式（３）中、Ｒ４は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１は２≦ｘ１≦４の数、ｘ２は０≦ｘ２≦２０の整数、ｘ３は０≦ｘ３≦２０の整数であり、０≦ｘ２＋ｘ３≦２０を満たし、ｙ１は０≦ｙ１≦３０の整数、ｚ１は０≦ｚ１≦１０の整数、ｙ２は０≦ｙ２≦３０の整数であり、ｚ２は０≦ｚ２≦１０の整数であり、ｚ１＋ｚ２＞０である。）
で示される分岐状オルガノハイドロジェンポリシロキサン：（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量、
（Ｃ）付加反応触媒：触媒量、及び
（Ｄ）下記一般式（２）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
（上記式（２）中、Ｒ３は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、Ｒ２は互いに独立に、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基であり、ｐは１≦ｐ≦２０の整数である。）：（Ａ）成分１００質量部に対し１０～６０質量部
を含有し、
前記付加硬化型フルオロシリコーン組成物が２３℃で液状であることを特徴とする付加硬化型フルオロシリコーン組成物である。 That is, a first aspect of the present invention is an addition-curable fluorosilicone composition,
(A) a compound represented by the following general formula (1):
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
a vinyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B) a compound represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in one molecule:
(In the above formula (3), R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms; and X is a divalent organic group. x1 is a number of 2≦x1≦4, x2 is an integer of 0≦x2≦20, and x3 is an integer of 0≦x3≦20, satisfying 0≦x2+x3≦20; y1 is an integer of 0≦y1≦30, z1 is an integer of 0≦z1≦10, y2 is an integer of 0≦y2≦30, z2 is an integer of 0≦z2≦10, and z1+z2>0.)
a branched organohydrogenpolysiloxane represented by the formula:
(C) an addition reaction catalyst: a catalytic amount; and (D) a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (2):
(In the above formula (2), R 3 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and R 2 's are each independently a group represented by the above R 3 or a 3,3,3-trifluoropropyl group, with the proviso that at least one R 2 is a 3,3,3-trifluoropropyl group, and p is an integer satisfying 1≦p≦20.): the compound contains 10 to 60 parts by mass per 100 parts by mass of component (A),
The addition-curable fluorosilicone composition is characterized in that the addition-curable fluorosilicone composition is liquid at 23°C.
（Ａ）下記一般式（１）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、
（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）
で示される分岐状オルガノハイドロジェンポリシロキサン：（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量、
（Ｃ）付加反応触媒：触媒量、及び
（Ｄ）下記一般式（２）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有し、
前記付加硬化型フルオロシリコーン組成物が２３℃で液状であることを特徴とする付加硬化型フルオロシリコーン組成物である。 That is, a first aspect of the present invention is an addition-curable fluorosilicone composition,
(A) a compound represented by the following general formula (1):
a vinyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B) a compound represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in one molecule:
a branched organohydrogenpolysiloxane represented by the formula:
(C) an addition reaction catalyst: a catalytic amount; and (D) a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (2):
The addition-curable fluorosilicone composition is characterized in that the addition-curable fluorosilicone composition is liquid at 23°C.
なお、本発明の第１態様のフルオロシリコーン組成物は、主剤として、フルオロアルキル基を有するジオルガノシロキサン単位の繰り返し構造が主鎖である直鎖状ポリシロキサンを含有する。一方、一般的なジメチルシリコーン組成物は、ジメチルシロキサン単位を繰り返し構造が主鎖である直鎖状ジメチルポリシロキサンを主剤とする。この点において、本発明の第１態様のフルオロシリコーン組成物は、ジメチルシリコーン組成物とは本質的に相違する。
The fluorosilicone composition of the first aspect of the present invention contains, as a base, a linear polysiloxane whose main chain is a repeating structure of diorganosiloxane units having fluoroalkyl groups. On the other hand, a typical dimethylsilicone composition contains, as a base, a linear dimethylpolysiloxane whose main chain is a repeating structure of dimethylsiloxane units. In this respect, the fluorosilicone composition of the first aspect of the present invention is essentially different from a dimethylsilicone composition.
また、上述のように、硬化性が非常に良好でありながら保存安定性にも優れ、機械的強度が保持されるフルオロシリコーンゴムを与えることができる、液状の付加硬化型フルオロシリコーン組成物の開発が求められていた。
Furthermore, as mentioned above, there was a need for the development of a liquid addition-curing fluorosilicone composition that could give a fluorosilicone rubber that has very good curing properties, excellent storage stability, and retains mechanical strength.
本発明者らは、上記課題について鋭意検討を重ねた結果、２３℃で液状である付加硬化型フルオロシリコーン組成物において、特定構造のアルケニル基含有オルガノポリシロキサンと、特定構造のハイドロジェンポリシロキサンとを用いることで、硬化性が良好で、機械的強度が保持されるフルオロシリコーンゴムを与えることができる液状付加硬化型フルオロシリコーン組成物となることを見出した。さらに、該液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形用材料として好適であることを見出した。本発明者らは、これらの知見に基づき、本発明の第２態様を完成させた。
As a result of intensive research into the above-mentioned problems, the present inventors have discovered that by using an alkenyl group-containing organopolysiloxane of a specific structure and a hydrogenpolysiloxane of a specific structure in an addition-curable fluorosilicone composition that is liquid at 23°C, a liquid addition-curable fluorosilicone composition can be obtained that can give a fluorosilicone rubber that has good curing properties and retains mechanical strength. Furthermore, they have discovered that this liquid addition-curable fluorosilicone composition is suitable as a material for injection molding, compression molding, and injection molding. Based on these findings, the present inventors have completed the second aspect of the present invention.
即ち、本発明の第２態様は、
液状付加硬化型フルオロシリコーン組成物であって、
（Ａ’）下記一般式（１Ａ）
（式中、Ｒ１は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは、互いに独立に、炭素数１～１０のパーフルオロアルキル基、又は３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基含有オルガノポリシロキサン、
（Ｂ’）下記一般式（２Ａ）
（上記式（２Ａ）中、Ｒ４は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆ’は、互いに独立に、炭素数１～１０のパーフルオロアルキル基、または３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１’は３≦ｘ１’≦５の整数であり、ｘ２’及びｘ３’は０≦ｘ２’＋ｘ３’≦２０の整数であり、ｙ１’は０≦ｙ１’≦３０の整数であり、ｙ２’は０≦ｙ２’≦３０の整数であり、ｚ１’は０≦ｚ１’≦１０の整数であり、ｚ２’は０≦ｚ２’≦１０の整数であり、ｗは０＜ｗ≦１０であり、ただし、ｘ２’、ｘ３’、ｙ１’、ｙ２’、ｚ１’及びｚ２’は同時に０とならない。）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサン：（Ｂ’）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合アルケニル基１個当たり０．５～１０となる量、
（Ｃ’）付加反応触媒：触媒量、及び
（Ｄ’）下記一般式（３Ａ）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
（上記式（３Ａ）中、Ｒ３は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、Ｒ２は、互いに独立に、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基であり、ｐは１≦ｐ≦２０の整数である）：（Ａ’）成分１００質量部に対し１０～６０質量部
を含有するものであることを特徴とする、２３℃で液状である、付加硬化型フルオロシリコーン組成物である。 That is, the second aspect of the present invention is
A liquid addition-curable fluorosilicone composition comprising:
(A') a compound represented by the following general formula (1A):
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
an alkenyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B') a compound represented by the following general formula (2A):
(In the above formula (2A), R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; and X is a divalent organic group. x1' is an integer of 3≦x1'≦5;x2' and x3' are integers of 0≦x2'+x3'≦20;y1' is an integer of 0≦y1'≦30;y2' is an integer of 0≦y2'≦30;z1' is an integer of 0≦z1'≦10;z2' is an integer of 0≦z2'≦10; and w is 0<w≦10, with the proviso that x2', x3', y1', y2', z1', and z2' are not simultaneously 0.)
an organohydrogenpolysiloxane having 3 to 5 silicon-bonded hydrogen atoms per molecule, represented by the formula:
(C') an addition reaction catalyst: a catalytic amount; and (D') a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (3A):
(In the above formula (3A), each R3 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and each R2 is independently a group represented by the above R3 or a 3,3,3-trifluoropropyl group, with the proviso that at least one R2 is a 3,3,3-trifluoropropyl group and p is an integer satisfying 1≦p≦20): An addition-curable fluorosilicone composition that is liquid at 23°C, characterized in that it contains 10 to 60 parts by mass of component (A') per 100 parts by mass of component (A').
液状付加硬化型フルオロシリコーン組成物であって、
（Ａ’）下記一般式（１Ａ）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基含有オルガノポリシロキサン、
（Ｂ’）下記一般式（２Ａ）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサン：（Ｂ’）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合アルケニル基１個当たり０．５～１０となる量、
（Ｃ’）付加反応触媒：触媒量、及び
（Ｄ’）下記一般式（３Ａ）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有するものであることを特徴とする、２３℃で液状である、付加硬化型フルオロシリコーン組成物である。 That is, the second aspect of the present invention is
A liquid addition-curable fluorosilicone composition comprising:
(A') a compound represented by the following general formula (1A):
an alkenyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B') a compound represented by the following general formula (2A):
an organohydrogenpolysiloxane having 3 to 5 silicon-bonded hydrogen atoms per molecule, represented by the formula:
(C') an addition reaction catalyst: a catalytic amount; and (D') a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (3A):
また、本発明の第２態様は、本発明の第２態様の付加硬化型フルオロシリコーン組成物の硬化物であることを特徴とするフルオロシリコーンゴムでもある。
The second aspect of the present invention is a fluorosilicone rubber that is a cured product of the addition-curable fluorosilicone composition of the second aspect of the present invention.
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。
The present invention is described in detail below, but is not limited to these.
［第１態様］
本発明の第１態様の付加硬化型フルオロシリコーン組成物は、（Ａ）特定の２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する特定の分岐状オルガノハイドロジェンポリシロキサン、（Ｃ）付加反応触媒、及び（Ｄ）特定の有機ケイ素化合物で表面処理した補強性シリカ充填剤を含有し、２３℃で液状であることを特徴とする。前記組成物は上記（Ａ）～（Ｄ）成分以外の成分を更に含んでもよい。以下、これら成分について説明する。 [First aspect]
The addition-curable fluorosilicone composition of the first aspect of the present invention is characterized in that it contains (A) a specific vinyl-containing organopolysiloxane having a viscosity of 100 to 500,000 mPa·s at 25° C., (B) a specific branched organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms per molecule, (C) an addition reaction catalyst, and (D) a reinforcing silica filler that has been surface-treated with a specific organosilicon compound, and is in a liquid state at 23° C. The composition may further contain components other than the above components (A) to (D). These components will be described below.
本発明の第１態様の付加硬化型フルオロシリコーン組成物は、（Ａ）特定の２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する特定の分岐状オルガノハイドロジェンポリシロキサン、（Ｃ）付加反応触媒、及び（Ｄ）特定の有機ケイ素化合物で表面処理した補強性シリカ充填剤を含有し、２３℃で液状であることを特徴とする。前記組成物は上記（Ａ）～（Ｄ）成分以外の成分を更に含んでもよい。以下、これら成分について説明する。 [First aspect]
The addition-curable fluorosilicone composition of the first aspect of the present invention is characterized in that it contains (A) a specific vinyl-containing organopolysiloxane having a viscosity of 100 to 500,000 mPa·s at 25° C., (B) a specific branched organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms per molecule, (C) an addition reaction catalyst, and (D) a reinforcing silica filler that has been surface-treated with a specific organosilicon compound, and is in a liquid state at 23° C. The composition may further contain components other than the above components (A) to (D). These components will be described below.
（Ａ）ビニル基含有オルガノポリシロキサン
（Ａ）成分は、下記一般式（１）で示される２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるオルガノポリシロキサンである。
（式中、Ｒ１は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である。）
(A) Vinyl Group-Containing Organopolysiloxane Component (A) is an organopolysiloxane represented by the following general formula (1) and having a viscosity at 25° C. of 100 to 500,000 mPa·s.
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, and a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
（Ａ）成分は、下記一般式（１）で示される２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるオルガノポリシロキサンである。
好ましくは下記式（１’）で示されるパーフルオロアルキル基含有オルガノポリシロキサンである。
（式中、Ｒ１は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、ｋは１～１０の整数であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である。）
Preferred is a perfluoroalkyl group-containing organopolysiloxane represented by the following formula (1').
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; k is an integer from 1 to 10; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
上記式（１）中、Ｒ１は互いに独立して、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、シクロヘキシル基等の炭素数１～８のアルキル基、フェニル基、トリル基等の炭素数６～１２のアリール基、ベンジル基などの炭素数７～１２のアラルキル基から選ばれる基であってよい。中でも、炭素数１～８のアルキル基が好ましく、特にメチル基であることが好ましい。
In the above formula (1), R 1 may be, independently of one another, a group selected from an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, etc., an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, etc., and an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, etc. Of these, an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is particularly preferred.
上記式（１）中、Ｒｆは互いに独立に、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基である。上記パーフルオロアルキル基としては、下記式
ＣｋＦ２ｋ＋１－ （ｋは１～１０の整数）
が例示される。また、上記パーフルオロポリエーテル基としては下記式
（ｓ、ｔはそれぞれ１～９の整数）
が例示される。 In the above formula (1), Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms. The perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10):
The perfluoropolyether group is exemplified by the following formula:
(s and t are integers from 1 to 9)
Examples are given below.
ＣｋＦ２ｋ＋１－ （ｋは１～１０の整数）
が例示される。また、上記パーフルオロポリエーテル基としては下記式
が例示される。 In the above formula (1), Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms. The perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10):
The perfluoropolyether group is exemplified by the following formula:
Examples are given below.
また、上記式（１）中、Ｘは２価の有機基である。Ｘは（Ａ）成分の直鎖状ビニル基含有オルガノポリシロキサンの主鎖と、側鎖のＲｆ基とをつなぐスペーサーとして機能し、Ｒｆ基どうし、又はＲｆ基と他の分子との間の相互作用を調整して、硬化物の炭化水素溶剤耐久性などの特性を望ましいものにすることができる。前記２価の有機基は特に限定されないが、炭素数２～４のアルキレン基であることができ、前記アルキレン基の水素原子の一部はフッ素原子などで置換されていてもよく、その途中又は末端に酸素原子、エステル結合又はアミド結合を有していてもよい。
In addition, in the above formula (1), X is a divalent organic group. X functions as a spacer that connects the main chain of the linear vinyl group-containing organopolysiloxane of component (A) with the Rf group in the side chain, and can adjust the interaction between the Rf groups or between the Rf group and other molecules to make the properties of the cured product, such as the hydrocarbon solvent resistance, desirable. The divalent organic group is not particularly limited, but can be an alkylene group having 2 to 4 carbon atoms, some of the hydrogen atoms of which may be substituted with fluorine atoms or the like, and may have an oxygen atom, an ester bond, or an amide bond in the middle or at the end.
この２価の有機基の例としては、下記式のようなものが例示される。
（＊はＲｆ基と結合し、＊＊はケイ素原子と結合する結合手）
Examples of this divalent organic group include those of the following formula:
(* is a bond to the Rf group, and ** is a bond to the silicon atom)
Ｒｆ－Ｘ基としては、ＣｋＦ２ｋ＋１－ＣＨ２ＣＨ２基（ｋは１～１０の整数）が好ましく、３，３，３－トリフルオロプロピル基（ｋは１）がより好ましい。
The Rf-X group is preferably a C k F 2k+1 -CH 2 CH 2 group (k is an integer of 1 to 10), and more preferably a 3,3,3-trifluoropropyl group (k is 1).
ｍは、０～１００の整数であり、好ましくは０～５０、より好ましくは０～３０、更に好ましくは０～２０、最も好ましくは０～１０の整数である。ｎは、１～８００の整数であり、好ましくは５～７５０、より好ましくは１０～６５０、更に好ましくは５０～６５０、最も好ましくは１００～６５０の整数である。ただし、（ｍ＋ｎ）は、５≦ｍ＋ｎ≦８００であり、好ましくは１０≦ｍ＋ｎ≦６８０、より好ましくは６０≦ｍ＋ｎ≦６８０、更に好ましくは１２０≦ｍ＋ｎ≦６８０の整数である。
m is an integer from 0 to 100, preferably from 0 to 50, more preferably from 0 to 30, even more preferably from 0 to 20, and most preferably from 0 to 10. n is an integer from 1 to 800, preferably from 5 to 750, more preferably from 10 to 650, even more preferably from 50 to 650, and most preferably from 100 to 650. However, (m+n) is an integer in the range of 5≦m+n≦800, preferably 10≦m+n≦680, more preferably 60≦m+n≦680, and even more preferably 120≦m+n≦680.
フルオロアルキル基を有するシロキサン単位の個数（すなわちｎの値）は、分子中の全シロキサン単位（特には、主鎖を構成する２官能性シロキサン単位の合計（すなわちｎ＋ｍ）に対して、好ましくは１０モル％以上、より好ましくは２０モル％以上、特に好ましくは３０～１００モル％であるのがよい。上限値は特に制限されず１００モル％以下であればよく、９５モル％以下、９０モル％以下、又は８０モル％以下であってもよい。この範囲であれば、優れた炭化水素溶剤耐久性を持たせることができるので好ましい。
The number of fluoroalkyl group-containing siloxane units (i.e., the value of n) is preferably 10 mol % or more, more preferably 20 mol % or more, and particularly preferably 30 to 100 mol %, of all siloxane units in the molecule (particularly the sum of the difunctional siloxane units constituting the main chain (i.e., n+m). The upper limit is not particularly limited as long as it is 100 mol % or less, and may be 95 mol % or less, 90 mol % or less, or 80 mol % or less. This range is preferable because it provides excellent hydrocarbon solvent resistance.
（Ａ）オルガノポリシロキサンの粘度は、２５℃における値が１００～５００，０００ｍＰａ・ｓとなる範囲であることを特徴とし、３００～１００，０００ｍＰａ・ｓの範囲内であることが好ましい。この範囲内であれば、硬化物の物理的特性が良好であり、また組成物の取扱い作業性が良好である。さらに、粘度が１００ｍＰａ・ｓ未満であると得られる硬化物の強度が不十分となり、５００，０００ｍＰａ・ｓを超えると組成物の取扱い性が低下するため好ましくない。なお、本発明の第１態様において、粘度はＪＩＳ Ｋ ７１１７－１：１９９９記載の方法で回転粘度計により測定した値である。（Ａ）オルガノポリシロキサンの重合度は２５℃における粘度が上記範囲となる値である。
The viscosity of the organopolysiloxane (A) is characterized by being in the range of 100 to 500,000 mPa·s at 25°C, and is preferably in the range of 300 to 100,000 mPa·s. Within this range, the physical properties of the cured product are good, and the handling and workability of the composition are good. Furthermore, if the viscosity is less than 100 mPa·s, the strength of the resulting cured product is insufficient, and if it exceeds 500,000 mPa·s, the handling of the composition decreases, which is not preferable. In the first embodiment of the present invention, the viscosity is a value measured with a rotational viscometer using the method described in JIS K 7117-1:1999. The degree of polymerization of the organopolysiloxane (A) is a value in which the viscosity at 25°C falls within the above range.
（Ｂ）オルガノハイドロジェンポリシロキサン
（Ｂ）成分は、ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）で示される分岐状オルガノハイドロジェンポリシロキサンである。該オルガノハイドロジェンポリシロキサンは、（Ａ）成分とヒドロシリル化付加反応し、硬化剤（架橋剤）として作用する。（Ｂ）成分の分子構造は、末端ハイドロジェン変性の分岐状シロキサンであり、該オルガノハイドロジェンシロキサンを含むことにより、フルオロシリコーン組成物は速硬化し、そのフルオロシリコーンゴム硬化物は高強度化することが可能になる。 (B) Organohydrogenpolysiloxane Component (B) is a branched organohydrogenpolysiloxane represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in each molecule. This organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A) and acts as a curing agent (crosslinking agent). The molecular structure of component (B) is a branched siloxane modified with terminal hydrogen, and by including this organohydrogensiloxane, the fluorosilicone composition cures quickly, and the fluorosilicone rubber cured product can have high strength.
（Ｂ）成分は、ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）で示される分岐状オルガノハイドロジェンポリシロキサンである。該オルガノハイドロジェンポリシロキサンは、（Ａ）成分とヒドロシリル化付加反応し、硬化剤（架橋剤）として作用する。（Ｂ）成分の分子構造は、末端ハイドロジェン変性の分岐状シロキサンであり、該オルガノハイドロジェンシロキサンを含むことにより、フルオロシリコーン組成物は速硬化し、そのフルオロシリコーンゴム硬化物は高強度化することが可能になる。 (B) Organohydrogenpolysiloxane Component (B) is a branched organohydrogenpolysiloxane represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in each molecule. This organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A) and acts as a curing agent (crosslinking agent). The molecular structure of component (B) is a branched siloxane modified with terminal hydrogen, and by including this organohydrogensiloxane, the fluorosilicone composition cures quickly, and the fluorosilicone rubber cured product can have high strength.
ケイ素原子に結合した水素原子以外のケイ素原子に結合する１価の有機基Ｒ４は、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、炭素数１～８、好ましくは炭素数１～６の、非置換又は置換の、アルケニル基等の脂肪族不飽和結合を含有しない１価炭化水素基が例示できる。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基が挙げられ、好ましくはメチル基である。（Ｂ）成分の１分子中のケイ素原子の数（（ｘ１＋ｘ２＋ｘ３＋ｙ１＋ｙ２＋ｚ１＋ｚ２）又は重合度）は、好ましくは４～６０個、より好ましくは４～５０個、更に好ましくは４～４０個である。
The monovalent organic group R4 bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and examples thereof include monovalent hydrocarbon groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, that do not contain an aliphatic unsaturated bond, such as an unsubstituted or substituted alkenyl group. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups, and preferably a methyl group. The number of silicon atoms in one molecule of component (B) ((x1+x2+x3+y1+y2+z1+z2) or the degree of polymerization) is preferably 4 to 60, more preferably 4 to 50, and even more preferably 4 to 40.
ケイ素原子に結合した水素原子以外のケイ素原子に結合する１価の有機基Ｒｆは、炭素数１～１０のパーフルオロアルキル基、及び炭素数３～３０のパーフルオロポリエーテル基から選ばれる基であり、上記式（１）のＲｆについて示した基が例示される。好ましくはパーフルオロアルキル基であり、より好ましくはトリフルオロメチル基である。
The monovalent organic group Rf bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms and a perfluoropolyether group having 3 to 30 carbon atoms, and examples thereof include the groups shown for Rf in formula (1) above. A perfluoroalkyl group is preferred, and a trifluoromethyl group is more preferred.
Ｘは２価の有機基であり、上記式（１）のＸについて示した基が例示される。
また、Ｒｆ－Ｘ基としては、ＣｋＦ２ｋ＋１－ＣＨ２ＣＨ２基（ｋは１～１０の整数）が好ましく、３，３，３－トリフルオロプロピル基（ｋは１）がより好ましい。 X is a divalent organic group, and examples thereof include the groups shown for X in formula (1) above.
As the Rf-X group, a C k F 2k+1 -CH 2 CH 2 group (k is an integer of 1 to 10) is preferable, and a 3,3,3-trifluoropropyl group (k is 1) is more preferable.
また、Ｒｆ－Ｘ基としては、ＣｋＦ２ｋ＋１－ＣＨ２ＣＨ２基（ｋは１～１０の整数）が好ましく、３，３，３－トリフルオロプロピル基（ｋは１）がより好ましい。 X is a divalent organic group, and examples thereof include the groups shown for X in formula (1) above.
As the Rf-X group, a C k F 2k+1 -CH 2 CH 2 group (k is an integer of 1 to 10) is preferable, and a 3,3,3-trifluoropropyl group (k is 1) is more preferable.
ｘ１は２≦ｘ１≦４の数、ｘ２は０≦ｘ２≦２０の整数、ｘ３は０≦ｘ３≦２０の整数であり、０≦ｘ２＋ｘ３≦２０を満たし、ｙ１は０≦ｙ１≦３０の整数、ｚ１は０≦ｚ１≦１０の整数、ｙ２は０≦ｙ２≦３０の整数であり、ｚ２は０≦ｚ２≦１０の整数であり、ｚ１＋ｚ２＞０である。ただし、ｘ２、ｘ３、ｙ１、ｙ２、ｚ１、及びｚ２は同時に０とならない。ｚ１＋ｚ２＞０であるため、上記式（３）で示される分岐状オルガノハイドロジェンポリシロキサンはＴ単位であるｚ１単位又はｚ２単位を１つ以上含む。
x1 is a number of 2≦x1≦4, x2 is an integer of 0≦x2≦20, x3 is an integer of 0≦x3≦20, and 0≦x2+x3≦20 is satisfied; y1 is an integer of 0≦y1≦30, z1 is an integer of 0≦z1≦10, y2 is an integer of 0≦y2≦30, z2 is an integer of 0≦z2≦10, and z1+z2>0. However, x2, x3, y1, y2, z1, and z2 are not all 0 at the same time. Since z1+z2>0, the branched organohydrogenpolysiloxane represented by the above formula (3) contains one or more z1 units or z2 units, which are T units.
（Ｂ）成分の具体例としては、下記分岐状オルガノハイドロジェンポリシロキサンを例示できるが、これらに限定されない。
Specific examples of the component (B) include, but are not limited to, the branched organohydrogenpolysiloxanes shown below.
（Ｂ）成分は室温（２５℃）で液状であるのがよい。該（Ｂ）成分の２５℃における粘度は０．１～１，０００ｍＰａ・ｓであることが好ましく、より好ましくは０．５～５００ｍＰａ・ｓ、更に好ましくは１～２００ｍＰａ・ｓである。粘度がこの範囲内であれば作業性が良好となる。
Component (B) should be liquid at room temperature (25°C). The viscosity of component (B) at 25°C is preferably 0.1 to 1,000 mPa·s, more preferably 0.5 to 500 mPa·s, and even more preferably 1 to 200 mPa·s. A viscosity within this range will ensure good workability.
（Ｂ）成分の量は、（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量である。つまり、前記組成物中のケイ素原子結合ビニル基（ＳｉＶｉ基）１個に対して（Ｂ）成分中のケイ素原子結合水素原子（ヒドロシリル基）の個数比が０．５～１０個、好ましくは１～５個の範囲内となる量である。（Ｂ）成分の量が上記下限値未満であると、得られる組成物は十分に硬化しない。また、（Ｂ）成分の配合量が上記上限値を超えると、得られるシリコーンゴムの耐熱性が極端に劣ったものとなる。尚、後述する（Ａ）成分以外のビニル基含有オルガノシロキサンなどのビニル基含有ケイ素化合物を含む場合は、組成物中のケイ素原子に結合するビニル基の個数に対する、該（Ｂ）成分のケイ素原子結合水素原子の個数比が上記範囲を満たせばよい。
なお、（Ｂ）成分は１種単独でも２種以上を併用してもよい。
さらに、上記式（３）で示される分岐状オルガノハイドロジェンポリシロキサンは、分子中に水酸基及び／またはアルコキシ基を含んでいてもよい。具体的には、水酸基及び／ または炭素数１から６のアルコキシ基を上記オルガノポリシロキサンの全置換基中の２０モル％以下の範囲内で含んでいてもよい。炭素数１から６のアルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｔ－ブトキシ基、ペンチルオキシ基、ネオペンチルオキシ基、ヘキシルオキシ基などが挙げられ、特にメトキシ基、エトキシ基、イソプロポキシ基が挙げられる。 The amount of component (B) is an amount such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.5 to 10 per silicon-bonded vinyl group in the composition. In other words, the ratio of the number of silicon-bonded hydrogen atoms (hydrosilyl groups) in component (B) to one silicon-bonded vinyl group (SiVi group) in the composition is within the range of 0.5 to 10, preferably 1 to 5. If the amount of component (B) is less than the lower limit, the resulting composition will not cure sufficiently. If the amount of component (B) exceeds the upper limit, the heat resistance of the resulting silicone rubber will be extremely poor. In addition, when a vinyl-containing silicon compound such as a vinyl-containing organosiloxane other than component (A) is included, as described below, it is sufficient that the ratio of the number of silicon-bonded hydrogen atoms in component (B) to the number of vinyl groups bonded to silicon atoms in the composition satisfies the above range.
The component (B) may be used alone or in combination of two or more types.
Furthermore, the branched organohydrogenpolysiloxane represented by formula (3) may contain hydroxyl groups and/or alkoxy groups in the molecule. Specifically, hydroxyl groups and/or alkoxy groups having 1 to 6 carbon atoms may be contained within a range of 20 mol % or less of all the substituents of the organopolysiloxane. Specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, t-butoxy groups, pentyloxy groups, neopentyloxy groups, and hexyloxy groups, and in particular methoxy groups, ethoxy groups, and isopropoxy groups.
なお、（Ｂ）成分は１種単独でも２種以上を併用してもよい。
さらに、上記式（３）で示される分岐状オルガノハイドロジェンポリシロキサンは、分子中に水酸基及び／またはアルコキシ基を含んでいてもよい。具体的には、水酸基及び／ または炭素数１から６のアルコキシ基を上記オルガノポリシロキサンの全置換基中の２０モル％以下の範囲内で含んでいてもよい。炭素数１から６のアルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｔ－ブトキシ基、ペンチルオキシ基、ネオペンチルオキシ基、ヘキシルオキシ基などが挙げられ、特にメトキシ基、エトキシ基、イソプロポキシ基が挙げられる。 The amount of component (B) is an amount such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.5 to 10 per silicon-bonded vinyl group in the composition. In other words, the ratio of the number of silicon-bonded hydrogen atoms (hydrosilyl groups) in component (B) to one silicon-bonded vinyl group (SiVi group) in the composition is within the range of 0.5 to 10, preferably 1 to 5. If the amount of component (B) is less than the lower limit, the resulting composition will not cure sufficiently. If the amount of component (B) exceeds the upper limit, the heat resistance of the resulting silicone rubber will be extremely poor. In addition, when a vinyl-containing silicon compound such as a vinyl-containing organosiloxane other than component (A) is included, as described below, it is sufficient that the ratio of the number of silicon-bonded hydrogen atoms in component (B) to the number of vinyl groups bonded to silicon atoms in the composition satisfies the above range.
The component (B) may be used alone or in combination of two or more types.
Furthermore, the branched organohydrogenpolysiloxane represented by formula (3) may contain hydroxyl groups and/or alkoxy groups in the molecule. Specifically, hydroxyl groups and/or alkoxy groups having 1 to 6 carbon atoms may be contained within a range of 20 mol % or less of all the substituents of the organopolysiloxane. Specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, t-butoxy groups, pentyloxy groups, neopentyloxy groups, and hexyloxy groups, and in particular methoxy groups, ethoxy groups, and isopropoxy groups.
（Ｃ）付加反応触媒
（Ｃ）成分の付加反応触媒は、前記組成物中のビニル基と（Ｂ）成分中のケイ素原子に結合した水素原子との付加反応を促進するものであればいかなる触媒であってもよい。通常は、白金族金属系触媒が好適に使用できる。例えば、白金、パラジウム、ロジウム等や塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサン又はアセチレン化合物との配位化合物、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等の、白金族金属又はそれらの化合物が挙げられるが、特に好ましくは白金系化合物である。（Ｃ）成分は、１種単独で用いても２種以上を併用してもよい。 (C) Addition reaction catalyst The addition reaction catalyst of the component (C) may be any catalyst that promotes the addition reaction between the vinyl group in the composition and the hydrogen atom bonded to the silicon atom in the component (B). Usually, platinum group metal catalysts are preferably used. For example, platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes or acetylene compounds, tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., platinum group metals or compounds thereof are listed, but platinum compounds are particularly preferred. The component (C) may be used alone or in combination of two or more.
（Ｃ）成分の付加反応触媒は、前記組成物中のビニル基と（Ｂ）成分中のケイ素原子に結合した水素原子との付加反応を促進するものであればいかなる触媒であってもよい。通常は、白金族金属系触媒が好適に使用できる。例えば、白金、パラジウム、ロジウム等や塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサン又はアセチレン化合物との配位化合物、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等の、白金族金属又はそれらの化合物が挙げられるが、特に好ましくは白金系化合物である。（Ｃ）成分は、１種単独で用いても２種以上を併用してもよい。 (C) Addition reaction catalyst The addition reaction catalyst of the component (C) may be any catalyst that promotes the addition reaction between the vinyl group in the composition and the hydrogen atom bonded to the silicon atom in the component (B). Usually, platinum group metal catalysts are preferably used. For example, platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes or acetylene compounds, tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., platinum group metals or compounds thereof are listed, but platinum compounds are particularly preferred. The component (C) may be used alone or in combination of two or more.
（Ｃ）成分の配合量は、触媒としての有効量（触媒量）でよいが、（Ａ）成分の量に対して、触媒金属元素（白金族金属元素）に換算して質量基準で、通常、０．５～１，０００ｐｐｍ、好ましくは１～５００ｐｐｍの範囲であり、１０～１００ｐｐｍの範囲であることがより好ましい。かかる範囲を満たすと、付加反応の反応速度が適切なものとなり、かつ硬化物の耐熱性が良好なものとなる。
The amount of component (C) to be blended may be an effective amount as a catalyst (catalytic amount), but is usually in the range of 0.5 to 1,000 ppm, preferably 1 to 500 ppm, and more preferably 10 to 100 ppm, by mass, converted into catalytic metal element (platinum group metal element) relative to the amount of component (A). If this range is satisfied, the reaction rate of the addition reaction will be appropriate, and the heat resistance of the cured product will be good.
（Ｄ）補強性シリカ充填剤
（Ｄ）成分は、下記式（２）で表される分子鎖両末端にシラノール基を有する直鎖状有機ケイ素化合物で表面処理した補強性シリカである。
上記式（２）中、Ｒ３は互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基から選ばれる基であり、例えば上記Ｒ１のために記載した例示が挙げられる。好ましくはメチル基である。Ｒ２は、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基である。ｐは１≦ｐ≦２０の整数であり、好ましくは３～９の整数である。
(D) Reinforcing Silica Filler Component (D) is a reinforcing silica that has been surface-treated with a linear organosilicon compound having silanol groups at both molecular chain terminals, as represented by the following formula (2).
In the above formula (2), R 3 is, independently of each other, a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and examples thereof include those described above for R 1. A methyl group is preferable. R 2 is a group represented by R 3 above, or a 3,3,3-trifluoropropyl group, with the proviso that at least one R 2 is a 3,3,3-trifluoropropyl group. p is an integer satisfying 1≦p≦20, and is preferably an integer from 3 to 9.
（Ｄ）成分は、下記式（２）で表される分子鎖両末端にシラノール基を有する直鎖状有機ケイ素化合物で表面処理した補強性シリカである。
本発明の第１態様において該補強性シリカ充填剤は、得られるシリコーンゴムに機械的強度を与えるために必須である。上記式（２）で表される有機ケイ素化合物が３，３，３－トリフルオロプロピル基を有さないと、得られる硬化物は引張強さ、切断時伸びや圧縮永久ひずみなどが劣る。
In the first embodiment of the present invention, the reinforcing silica filler is essential for imparting mechanical strength to the resulting silicone rubber. If the organosilicon compound represented by the above formula (2) does not have a 3,3,3-trifluoropropyl group, the resulting cured product will have inferior tensile strength, elongation at break, compression set, etc.
上記分子鎖両末端がシラノール基で封鎖された直鎖状有機ケイ素化合物で表面処理された補強性シリカ充填剤を含有することで、本組成物の粘度及び加熱硬化後のゴムの圧縮永久ひずみを低くすることができる。
上記補強性シリカ充填剤としては、従来からシリコーンゴム組成物に使用されているものを用いることができ、沈澱シリカ（湿式シリカ）、ヒュームドシリカ（乾式シリカ）、焼成シリカ等が好適である。特にはヒュームドシリカが好適である。 By containing the above-mentioned reinforcing silica filler that has been surface-treated with a linear organosilicon compound having both molecular chain terminals blocked with silanol groups, it is possible to reduce the viscosity of the composition and the compression set of the rubber after heat curing.
As the reinforcing silica filler, those conventionally used in silicone rubber compositions can be used, and precipitated silica (wet silica), fumed silica (dry silica), fired silica, etc. are preferred. Fumed silica is particularly preferred.
上記補強性シリカ充填剤としては、従来からシリコーンゴム組成物に使用されているものを用いることができ、沈澱シリカ（湿式シリカ）、ヒュームドシリカ（乾式シリカ）、焼成シリカ等が好適である。特にはヒュームドシリカが好適である。 By containing the above-mentioned reinforcing silica filler that has been surface-treated with a linear organosilicon compound having both molecular chain terminals blocked with silanol groups, it is possible to reduce the viscosity of the composition and the compression set of the rubber after heat curing.
As the reinforcing silica filler, those conventionally used in silicone rubber compositions can be used, and precipitated silica (wet silica), fumed silica (dry silica), fired silica, etc. are preferred. Fumed silica is particularly preferred.
（Ｄ）成分は、表面未処理のシリカを予め上記式（２）の有機ケイ素化合物で表面処理したものである。あるいは、表面未処理のシリカとポリシロキサン分（すなわち（Ａ）成分）とを混練し、上記式（２）の有機ケイ素化合物を添加して、好ましくは少量の水の存在下に、加熱混合して混合物中で表面処理してもよい。また、本発明の第１態様で用いる表面未処理のシリカとは、上記式（２）の有機ケイ素化合物で表面処理していないものをいい、ジメチルジクロロシラン等で表面処理された乾式シリカ（例えば、アエロジルＲ－９７４等）であってもよい。このようにジメチルジクロロシラン等で表面処理された乾式シリカの表面を、上記式（２）有機ケイ素化合物でさらに処理するのが好ましい。
The (D) component is a surface-untreated silica that has been previously surface-treated with the organosilicon compound of formula (2). Alternatively, the surface-untreated silica may be kneaded with a polysiloxane component (i.e., component (A)), and the organosilicon compound of formula (2) may be added, and the mixture may be heated and mixed, preferably in the presence of a small amount of water, to perform surface treatment in the mixture. The surface-untreated silica used in the first aspect of the present invention refers to silica that has not been surface-treated with the organosilicon compound of formula (2), and may be dry silica (e.g., Aerosil R-974, etc.) that has been surface-treated with dimethyldichlorosilane or the like. It is preferable to further treat the surface of the dry silica that has been surface-treated with dimethyldichlorosilane or the like in this way with the organosilicon compound of formula (2).
上記式（２）の有機ケイ素化合物によりシリカを表面処理する際の処理量は、上記式（２）の有機ケイ素化合物で表面処理する前のシリカ４０質量部に対して上記式（２）の有機ケイ素化合物を１～３０質量部、特に２～２０質量部で表面処理することが好ましい。
When surface treating silica with the organosilicon compound of formula (2), the amount of the organosilicon compound of formula (2) is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 40 parts by mass of silica before surface treatment with the organosilicon compound of formula (2).
また、上記式（２）の有機ケイ素化合物以外の、オルガノシランやオルガノシラザンを表面処理剤として併用してもよい。オルガノシランの例としては、トリメチルクロロシラン、ジメチルジクロロシラン、ジメチルビニルクロロシラン、トリビニルクロロシランなどのクロロシラン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス（メトキシエトキシ）シラン、などのアルコキシシラン類、ヘキサメチルジシラザン、ヘキサメチルシクロトリシラザン、１，３－ジビニル－１，１，３，３－テトラメチルジシラザンなどのシラザン類などが挙げられ、中でも、ヘキサメチルジシラザン、１，３－ジビニル－１，１，３，３－テトラメチルジシラザンなどが好ましい。これらのオルガノシランやオルガノシラザンの処理量は、表面未処理のシリカ４０質量部に対して０．１～１５質量部、特に０．１～１０質量部で表面処理することが好ましい。
In addition, organosilanes and organosilazanes other than the organosilicon compound of formula (2) above may be used in combination as surface treatment agents. Examples of organosilanes include chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, and trivinylchlorosilane; alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, and vinyltris(methoxyethoxy)silane; and silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, and 1,3-divinyl-1,1,3,3-tetramethyldisilazane. Of these, hexamethyldisilazane and 1,3-divinyl-1,1,3,3-tetramethyldisilazane are preferred. The amount of these organosilanes or organosilazanes used for surface treatment is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 40 parts by mass of untreated silica.
上記式（２）の有機ケイ素化合物で表面処理する前のシリカのＢＥＴ法による比表面積は、５０ｍ２／ｇ以上、好ましくは１００～４００ｍ２／ｇ、より好ましくは１５０～３５０ｍ２／ｇである。比表面積が５０ｍ２／ｇ以上であれば十分な強度が得られ、ゴム成形品の外観も良くなる。４００ｍ２／ｇ以下であれば配合が容易である。表面処理後のシリカのＢＥＴ法による比表面積も、上記範囲内にあればよい。
The BET specific surface area of the silica before surface treatment with the organosilicon compound of formula (2) is 50 m 2 /g or more, preferably 100 to 400 m 2 /g, and more preferably 150 to 350 m 2 /g. If the specific surface area is 50 m 2 /g or more, sufficient strength is obtained and the appearance of the rubber molded product is also improved. If it is 400 m 2 /g or less, compounding is easy. The BET specific surface area of the silica after surface treatment may also be within the above range.
（Ｄ）成分の配合量は、（Ａ）成分１００質量部に対し、１０～６０質量部、好ましくは１５～５５質量部である。配合量が上記下限値未満では、得られるシリコーンゴムが十分なゴム強度を有さず、また上記上限値を超えると組成物中への配合が困難になる。
The amount of component (D) to be blended is 10 to 60 parts by mass, and preferably 15 to 55 parts by mass, per 100 parts by mass of component (A). If the blending amount is less than the lower limit, the resulting silicone rubber will not have sufficient rubber strength, and if the blending amount exceeds the upper limit, it will be difficult to blend the silicone rubber into the composition.
その他の成分
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、前記（Ａ）～（Ｄ）成分以外のその他の成分を必要に応じて含有してもよい。その他の成分とは例えば、カーボンブラック、導電性亜鉛華、金属粉等の導電剤、窒素含有化合物、エチニルシクロヘキサノールなどのアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、酸化鉄、酸化セリウムのような耐熱性付与剤、トリアゾール化合物、ベンゾトリアゾールシランなどのベンゾトリアゾール誘導体等の圧縮永久ひずみ向上剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤、チクソ性付与剤等が挙げられる。ただし、本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は一分子中にトリアルコキシ基を３個有するイソシアヌル酸誘導体を含有しない。 Other components The liquid addition curable fluorosilicone composition of the first embodiment of the present invention may contain other components other than the components (A) to (D) as necessary. Examples of other components include conductive agents such as carbon black, conductive zinc oxide, and metal powder, nitrogen-containing compounds, acetylene compounds such as ethynylcyclohexanol, hydrosilylation reaction inhibitors such as phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds, heat resistance imparting agents such as iron oxide and cerium oxide, compression set improvers such as triazole compounds and benzotriazole derivatives such as benzotriazole silane, internal release agents such as dimethyl silicone oil, adhesion imparting agents, and thixotropy imparting agents. However, the liquid addition curable fluorosilicone composition of the first embodiment of the present invention does not contain an isocyanuric acid derivative having three trialkoxy groups in one molecule.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、前記（Ａ）～（Ｄ）成分以外のその他の成分を必要に応じて含有してもよい。その他の成分とは例えば、カーボンブラック、導電性亜鉛華、金属粉等の導電剤、窒素含有化合物、エチニルシクロヘキサノールなどのアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、酸化鉄、酸化セリウムのような耐熱性付与剤、トリアゾール化合物、ベンゾトリアゾールシランなどのベンゾトリアゾール誘導体等の圧縮永久ひずみ向上剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤、チクソ性付与剤等が挙げられる。ただし、本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は一分子中にトリアルコキシ基を３個有するイソシアヌル酸誘導体を含有しない。 Other components The liquid addition curable fluorosilicone composition of the first embodiment of the present invention may contain other components other than the components (A) to (D) as necessary. Examples of other components include conductive agents such as carbon black, conductive zinc oxide, and metal powder, nitrogen-containing compounds, acetylene compounds such as ethynylcyclohexanol, hydrosilylation reaction inhibitors such as phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds, heat resistance imparting agents such as iron oxide and cerium oxide, compression set improvers such as triazole compounds and benzotriazole derivatives such as benzotriazole silane, internal release agents such as dimethyl silicone oil, adhesion imparting agents, and thixotropy imparting agents. However, the liquid addition curable fluorosilicone composition of the first embodiment of the present invention does not contain an isocyanuric acid derivative having three trialkoxy groups in one molecule.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、上記（Ａ）～（Ｄ）成分、及び必要に応じて各任意成分を、ニーダー、プラネタリーミキサーなどの通常の混合撹拌器、混練器等を用いて上記各成分を均一に混合することにより調製することができる。
The liquid addition-curable fluorosilicone composition of the first aspect of the present invention can be prepared by uniformly mixing the above components (A) to (D) and, if necessary, each optional component, using a conventional mixer, stirrer, kneader, or other such device as a kneader or planetary mixer.
本発明の第１態様の組成物は２３℃で液状であることが特徴である。ここで、「２３℃で液状である」とは、２３℃において一定の体積を有するが、容器の形状に従って形が変化する（流動性を有する）状態であることをいう。作業性等の点から、２３℃において、せん断速度１０ｓ－１での粘度が１，５００Ｐａ・ｓ以下であることが好ましく、より好ましくは１００～１，２００Ｐａ・ｓ、更に好ましくは２００～１，１００Ｐａ・ｓである。この粘度が１，５００Ｐａ・ｓを超える場合には、注入、圧縮及び射出成形を行う際に材料供給に時間がかかり、生産性が著しく低下することがある。なお、本発明の第１態様において、上記せん断速度下での粘度の測定は、精密回転式粘度計（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ製）を用いて行ったものである。
The composition of the first aspect of the present invention is characterized in that it is liquid at 23°C. Here, "liquid at 23°C" means that it has a certain volume at 23°C, but changes shape (has fluidity) according to the shape of the container. From the viewpoint of workability, etc., the viscosity at 23°C and a shear rate of 10s -1 is preferably 1,500 Pa·s or less, more preferably 100 to 1,200 Pa·s, and even more preferably 200 to 1,100 Pa·s. If the viscosity exceeds 1,500 Pa·s, it may take a long time to supply the material when performing injection, compression, and injection molding, and productivity may be significantly reduced. In the first aspect of the present invention, the viscosity at the above shear rate was measured using a precision rotational viscometer (manufactured by Thermo Fisher Scientific).
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は２液型とすることもできる。この場合、架橋剤としての（Ｂ）成分と付加反応触媒の（Ｃ）成分とが同一の組成物（Ａ液又はＢ液）中に混在しないように各成分を適宜分割すればよく、例えば、（Ａ）成分、（Ｃ）成分及び（Ｄ）成分を含有するＡ液と、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分を含有するＢ液とからなる２液型の組成物とすることができ、等質量又は等容量で混合できるように調製することが好ましい。
The liquid addition-curable fluorosilicone composition of the first aspect of the present invention can also be a two-liquid type. In this case, each component can be appropriately divided so that the crosslinking agent (B) and the addition reaction catalyst (C) are not mixed in the same composition (liquid A or B). For example, a two-liquid type composition can be made consisting of liquid A containing components (A), (C), and (D), and liquid B containing components (A), (B), and (D), and it is preferable to prepare it so that they can be mixed in equal masses or volumes.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形、射出成形等各種の成形方法に適用することができる。以下、注入成形、圧縮成形、又は射出成形によるフルオロシリコーンゴムの成形方法について詳細に説明する。
The liquid addition-curable fluorosilicone composition of the first aspect of the present invention can be applied to various molding methods such as injection molding, compression molding, and injection molding. Below, the molding method of fluorosilicone rubber by injection molding, compression molding, or injection molding will be explained in detail.
注入成形の場合、液状付加硬化型フルオロシリコーン組成物は、Ａ液とＢ液の２液タイプに分割される。２液に分割された材料は各Ａ液及びＢ液を等量混合し、金属金型内に注入され、恒温槽で加熱されて硬化し、シリコーンゴムが成形される。圧縮成形の場合、プレス機などの圧縮機に金属金型を設置し、注入成形と同様に上記Ａ液及びＢ液を等量混合し、金型に注入され、加熱されて硬化し、シリコーンゴムが成形される。射出成形の場合、各Ａ液及びＢ液が材料供給ポンプから定量器に供給される。定量器からＡ液とＢ液が等量の割合で材料供給ラインを通じて合流する。材料は成形機本体のスクリュー部とシリンダー部で混合される。その後、金型に射出され、金型内で加熱されて硬化し、シリコーンゴムが成形される。
In the case of injection molding, the liquid addition-curing fluorosilicone composition is divided into two liquid types, liquid A and liquid B. The two liquids are mixed in equal amounts and injected into a metal mold, where they are heated and cured in a thermostatic bath to form silicone rubber. In the case of compression molding, a metal mold is placed on a compressor such as a press, and equal amounts of the above liquids A and B are mixed in the same way as in injection molding, injected into the mold, where they are heated and cured to form silicone rubber. In the case of injection molding, liquid A and liquid B are supplied from the material supply pump to a metering machine. From the metering machine, liquid A and liquid B are merged in equal amounts through the material supply line. The material is mixed in the screw and cylinder parts of the molding machine body. It is then injected into a mold, where it is heated and cured to form silicone rubber.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、特に液状シリコーンゴム射出成形システム（ＬＩＭＳ：Ｌｉｑｕｉｄ Ｉｎｊｅｃｔｉｏｎ Ｍｏｌｄｉｎｇ Ｓｙｓｔｅｍ）に適している。ＬＩＭＳは、優れた特性を持つ液状シリコーンゴムと、これを精密・安定的に射出する成形機とを組み合わせた成形加工システムであり、混合から成形までをすべて自動化でき、工程の簡略化・短縮化をはかりながら、高品質な製品の成形を容易にすることができる。この成形法において本発明の第１態様の組成物は以下のような有利な点を有する。即ち、（ｉ）硬化速度が速く、成形時間を短縮化できるので工程の短縮化が可能であり、（ｉｉ）材料が液状であるため、低射出圧での成形が可能で、精密な部品の成形にも対応できるため、生産性が向上し、（ｉｉｉ）ノーバリ、ランナーレス成形に対応でき、さらに硬化後の離型性にも優れることから、成形工程を自動化することができ、（ｉｖ）硬化反応による副生成物がなく、またノーバリ、ランナーレス成形によって廃材の処理が不要なため、環境に配慮した製造が可能である。
The liquid addition-curable fluorosilicone composition of the first aspect of the present invention is particularly suitable for liquid silicone rubber injection molding systems (LIMS: Liquid Injection Molding System). LIMS is a molding processing system that combines liquid silicone rubber, which has excellent properties, with a molding machine that precisely and stably injects it, and can automate everything from mixing to molding, simplifying and shortening the process while facilitating the molding of high-quality products. In this molding method, the composition of the first aspect of the present invention has the following advantages: That is, (i) the curing speed is fast, and molding time can be shortened, which allows for shortening of the process; (ii) since the material is liquid, molding can be performed at low injection pressure, and precision parts can also be molded, improving productivity; (iii) since it is compatible with flash-free and runnerless molding and has excellent release properties after curing, the molding process can be automated; and (iv) since there are no by-products from the curing reaction, and since flash-free and runnerless molding eliminates the need for waste disposal, environmentally friendly manufacturing is possible.
本発明の第１態様は、上記付加硬化型フルオロシリコーン組成物の硬化物であるフルオロシリコーンゴムを提供する。このようなフルオロシリコーンゴムであれば、良好な機械的強度を保持できる。組成物の硬化は公知技術に従って行えばよく、硬化方法・条件は特に限定されない。
The first aspect of the present invention provides a fluorosilicone rubber that is a cured product of the above-mentioned addition-curable fluorosilicone composition. Such a fluorosilicone rubber can maintain good mechanical strength. The composition can be cured according to known techniques, and there are no particular limitations on the curing method or conditions.
液状付加硬化型フルオロシリコーン組成物の硬化成形（１次キュア）条件としては、公知の付加反応硬化型シリコーン組成物と同様でよく、硬化温度は８０～２２０℃、特に１２０～２００℃で、硬化時間は３秒～１０分間、特に５秒～５分間加熱することにより硬化成形することができる。成形した硬化物は、必要に応じて、例えば、１８０～２２０℃で３０分～６時間程度、ポストキュア（２次硬化）させてもよい。
The conditions for hardening and molding (primary cure) of the liquid addition-curing fluorosilicone composition may be the same as those for known addition-reaction-curing silicone compositions, and the composition can be hardened and molded by heating at a hardening temperature of 80-220°C, particularly 120-200°C, and for a hardening time of 3 seconds to 10 minutes, particularly 5 seconds to 5 minutes. If necessary, the molded cured product may be post-cured (secondary cure), for example, at 180-220°C for about 30 minutes to 6 hours.
本願液状付加硬化型フルオロシリコーン組成物から得られる硬化物（シリコーンゴム）は、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき測定される、１８０℃で２２時間圧縮後の圧縮永久ひずみが１０％以下であり、かつ、機械的強度の引張強さが５．０ＭＰａ以上である。または、ＪＩＳ Ｋ ６２４９：２００３に基づく、圧縮率２５％にて１８０℃で２２時間圧縮後の圧縮永久ひずみが１５％以下、好ましくは１０％以下となるのがよい。圧縮永久ひずみが１０％以下の場合、硬化物は、シール材、Ｏ－ｒｉｎｇ、又はパッキンなどの部品（成形体）として使用できる。機械的強度はゴム成形品の実用強度の点から、引張強さが４．５ＭＰａ以上、好ましくは５．０ＭＰａ以上であるのがよい。
The cured product (silicone rubber) obtained from the liquid addition-curable fluorosilicone composition of the present invention has a compression set of 10% or less after 22 hours of compression at 180°C, and a mechanical strength of tensile strength of 5.0 MPa or more, as measured according to the description of JIS K 6249:2003. Alternatively, the compression set of the cured product after 22 hours of compression at 180°C at a compression rate of 25%, as measured according to JIS K 6249:2003, should be 15% or less, preferably 10% or less. When the compression set is 10% or less, the cured product can be used as a part (molded product) such as a sealing material, O-ring, or packing. From the viewpoint of practical strength of rubber molded products, the mechanical strength should be tensile strength of 4.5 MPa or more, preferably 5.0 MPa or more.
また、本発明の第１態様は上記フルオロシリコーンゴムの成形体であることを特徴とするフルオロシリコーンゴム成形品を提供する。
The first aspect of the present invention provides a fluorosilicone rubber molded article, which is a molded article of the above-mentioned fluorosilicone rubber.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物を加熱硬化して得られたフルオロシリコーンゴム成形品は、耐ガソリン性、耐油性に優れることから、航空機や車載用ゴム部品、プリンター部品等又、近年、皮脂耐性の点からモバイル部品や耐酸性の点から燃料電池車用シール部品にも好適に用いることができる。
The fluorosilicone rubber molded products obtained by heat curing the liquid addition-curable fluorosilicone composition of the first aspect of the present invention have excellent gasoline and oil resistance, and are therefore suitable for use in aircraft and automotive rubber parts, printer parts, etc. In recent years, they have also been used in mobile parts due to their sebum resistance, and in sealing parts for fuel cell vehicles due to their acid resistance.
［第２態様］
［液状付加硬化型フルオロシリコーン組成物］
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、概して、（Ａ’）アルケニル基含有オルガノポリシロキサンと、（Ｂ’）オルガノハイドロジェンポリシロキサンと、（Ｃ’）付加反応触媒と、（Ｄ’）補強性シリカ充填剤とを含む。 [Second aspect]
[Liquid addition-curable fluorosilicone composition]
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention generally comprises (A') an alkenyl-containing organopolysiloxane, (B') an organohydrogenpolysiloxane, (C') an addition reaction catalyst, and (D') a reinforcing silica filler.
［液状付加硬化型フルオロシリコーン組成物］
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、概して、（Ａ’）アルケニル基含有オルガノポリシロキサンと、（Ｂ’）オルガノハイドロジェンポリシロキサンと、（Ｃ’）付加反応触媒と、（Ｄ’）補強性シリカ充填剤とを含む。 [Second aspect]
[Liquid addition-curable fluorosilicone composition]
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention generally comprises (A') an alkenyl-containing organopolysiloxane, (B') an organohydrogenpolysiloxane, (C') an addition reaction catalyst, and (D') a reinforcing silica filler.
以下、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物における各成分についてより詳細に説明する。
The components of the liquid addition-curable fluorosilicone composition according to the second aspect of the present invention are described in more detail below.
（Ａ’）アルケニル基含有オルガノポリシロキサン
（Ａ’）成分は、下記一般式（１Ａ）で示される２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基（ビニル基）含有オルガノポリシロキサンである。
（式中、Ｒ１は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆは、互いに独立に、炭素数１～１０のパーフルオロアルキル基、又は３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である）
(A') Alkenyl Group-Containing Organopolysiloxane Component (A') is an alkenyl group (vinyl group)-containing organopolysiloxane represented by the following general formula (1A) and having a viscosity at 25°C of 100 to 500,000 mPa·s.
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; X is a divalent organic group; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
（Ａ’）成分は、下記一般式（１Ａ）で示される２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基（ビニル基）含有オルガノポリシロキサンである。
（Ａ’）成分は、好ましくは下記式（１Ａ’）
（式中、Ｒ１は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、ｋは１～１０の整数であり、ｍは０～１００の整数であり、ｎは１～８００の整数であり、ただし、５≦ｍ＋ｎ≦８００である）
で示されるパーフルオロアルキル基含有オルガノポリシロキサンである。 The component (A') is preferably represented by the following formula (1A'):
(In the formula, R1 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; k is an integer from 1 to 10; m is an integer from 0 to 100; and n is an integer from 1 to 800, with the proviso that 5≦m+n≦800.)
The organopolysiloxane has a perfluoroalkyl group and is represented by the formula:
で示されるパーフルオロアルキル基含有オルガノポリシロキサンである。 The component (A') is preferably represented by the following formula (1A'):
The organopolysiloxane has a perfluoroalkyl group and is represented by the formula:
上記式（１Ａ）及び式（１Ａ’）中、Ｒ１は、互いに独立して、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、及びシクロヘキシル基等の炭素数１～８のアルキル基、フェニル基、及びトリル基等の炭素数６～１２のアリール基、ベンジル基などの炭素数７～１２のアラルキル基から選ばれる基である。中でも、炭素数１～８のアルキル基が好ましく、特にメチル基であることが好ましい。
In the above formula (1A) and formula (1A'), R 1 is, independently of each other, a group selected from alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group, aryl groups having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, and an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group. Among these, an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is particularly preferred.
上記式（１Ａ）中、Ｒｆは、互いに独立に、炭素数１～１０のパーフルオロアルキル基、又は３～３０のパーフルオロポリエーテル基から選ばれる基である。上記パーフルオロアルキル基としては、下記式
ＣｋＦ２ｋ＋１－ （ｋは１～１０の整数である）
が例示される。 In the above formula (1A), Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms. The perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10).
Examples are given below.
ＣｋＦ２ｋ＋１－ （ｋは１～１０の整数である）
が例示される。 In the above formula (1A), Rf's are each independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms. The perfluoroalkyl group is represented by the following formula: C k F 2k+1 - (k is an integer of 1 to 10).
Examples are given below.
また、上記パーフルオロポリエーテル基としては、下記式
（ｓ、ｔはそれぞれ１～９の整数である）
が例示される。 The perfluoropolyether group may be represented by the following formula:
(s and t are each an integer from 1 to 9)
Examples are given below.
が例示される。 The perfluoropolyether group may be represented by the following formula:
Examples are given below.
また、上記式（１Ａ）中、Ｘは２価の有機基である。この２価の有機基の例としては、下記式のようなものが例示される。
（＊はＲｆ基と結合する結合手であり、＊＊はケイ素原子と結合する結合手である）
In the above formula (1A), X is a divalent organic group. Examples of the divalent organic group include those represented by the following formula:
(* is a bond bonded to the Rf group, and ** is a bond bonded to the silicon atom)
ｍは、０～１００の整数であり、好ましくは０～５０、より好ましくは０～３０、更に好ましくは０～２０、最も好ましくは０～１０の整数である。ｎは、１～８００の整数であり、好ましくは５～７５０、より好ましくは１０～６５０、更に好ましくは５０～６５０、最も好ましくは１００～６５０の整数である。ただし、（ｍ＋ｎ）は、５≦ｍ＋ｎ≦８００であり、好ましくは１０≦ｍ＋ｎ≦６８０、より好ましくは６０≦ｍ＋ｎ≦６８０、更に好ましくは１２０≦ｍ＋ｎ≦６８０の整数である。
m is an integer from 0 to 100, preferably from 0 to 50, more preferably from 0 to 30, even more preferably from 0 to 20, and most preferably from 0 to 10. n is an integer from 1 to 800, preferably from 5 to 750, more preferably from 10 to 650, even more preferably from 50 to 650, and most preferably from 100 to 650. However, (m+n) is an integer in the range of 5≦m+n≦800, preferably 10≦m+n≦680, more preferably 60≦m+n≦680, and even more preferably 120≦m+n≦680.
（Ａ’）成分のオルガノポリシロキサンの粘度は、２５℃における値が１００～５００，０００ｍＰａ・ｓとなる範囲であることを特徴とし、３００～１００，０００ｍＰａ・ｓの範囲内であることが好ましい。この範囲内であれば、硬化物の物理的特性が良好であり、また組成物の取扱い作業性が良好である。さらに、粘度が１００ｍＰａ・ｓ未満であると得られる硬化物の強度が不十分となり、５００，０００ｍＰａ・ｓを超えると組成物の取扱い性が低下するため好ましくない。なお、本発明の第２態様において、粘度はＪＩＳ Ｋ ７１１７－１：１９９９記載の方法で回転粘度計により測定した値である。（Ａ’）オルガノポリシロキサンの重合度は２５℃における粘度が上記範囲となる値である。
The viscosity of the organopolysiloxane of component (A') is characterized by being in the range of 100 to 500,000 mPa·s at 25°C, and is preferably in the range of 300 to 100,000 mPa·s. Within this range, the physical properties of the cured product are good, and the handling and workability of the composition are good. Furthermore, if the viscosity is less than 100 mPa·s, the strength of the resulting cured product is insufficient, and if it exceeds 500,000 mPa·s, the handling of the composition is reduced, which is not preferable. In the second embodiment of the present invention, the viscosity is a value measured with a rotational viscometer using the method described in JIS K 7117-1:1999. The degree of polymerization of organopolysiloxane (A') is a value in which the viscosity at 25°C falls within the above range.
パーフルオロアルキル基又はパーフルオロポリエーテル基を有するシロキサン単位の個数（すなわちｎの値）は、分子中の全シロキサン単位（特には、主鎖を構成する２官能性シロキサン単位の合計（すなわちｎ＋ｍ）に対して、好ましくは１０モル％以上、より好ましくは２０モル％以上、特に好ましくは３０～１００モル％であるのがよい。上限値は特に制限されず１００モル％以下であればよく、９５モル％以下、９０モル％以下、又は８０モル％以下であってもよい。この範囲であれば、優れた炭化水素溶剤耐久性を持たせることができるので好ましい。
The number of siloxane units having a perfluoroalkyl group or a perfluoropolyether group (i.e., the value of n) is preferably 10 mol % or more, more preferably 20 mol % or more, and particularly preferably 30 to 100 mol %, of all siloxane units in the molecule (particularly the sum of the bifunctional siloxane units constituting the main chain (i.e., n + m). The upper limit is not particularly limited as long as it is 100 mol % or less, and may be 95 mol % or less, 90 mol % or less, or 80 mol % or less. This range is preferable because it can provide excellent hydrocarbon solvent resistance.
なお、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、主剤として、パーフルオロアルキル基又はパーフルオロポリエーテル基を有するジオルガノシロキサン単位の繰り返し構造が主鎖である直鎖状ポリシロキサンを含有する。一方、一般的なジメチルシリコーン組成物は、ジメチルシロキサン単位を繰り返し構造が主鎖である直鎖状ジメチルポリシロキサンを主剤とする。この点において、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、ジメチルシリコーン組成物とは本質的に相違する。
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention contains as a base a linear polysiloxane whose main chain is a repeating structure of diorganosiloxane units having perfluoroalkyl groups or perfluoropolyether groups. On the other hand, a typical dimethylsilicone composition contains as a base a linear dimethylpolysiloxane whose main chain is a repeating structure of dimethylsiloxane units. In this respect, the liquid addition-curable fluorosilicone composition of the second aspect of the present invention is essentially different from a dimethylsilicone composition.
（Ｂ’）オルガノハイドロジェンポリシロキサン
（Ｂ’）成分であるオルガノハイドロジェンポリシロキサンは、下記式（２Ａ）
（上記式（２Ａ）中、Ｒ４は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｒｆ’は、互いに独立に、炭素数１～１０のパーフルオロアルキル基、または３～３０のパーフルオロポリエーテル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１’は３≦ｘ１’≦５の整数であり、ｘ２’及びｘ３’は０≦ｘ２’＋ｘ３’≦２０の整数であり、ｙ１’は０≦ｙ１’≦３０の整数であり、ｙ２’は０≦ｙ２’≦３０の整数であり、ｚ１’は０≦ｚ１’≦１０の整数であり、ｚ２’は０≦ｚ２’≦１０の整数であり、ｗは０＜ｗ≦１０であり、ただし、ｘ２’、ｘ３’、ｙ１’、ｙ２’、ｚ１’及びｚ２’は同時に０とならない。）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサンである。 (B') Organohydrogenpolysiloxane The organohydrogenpolysiloxane of the component (B') is represented by the following formula (2A):
(In the above formula (2A), R 4 is independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Rf' is independently a group selected from a perfluoroalkyl group having 1 to 10 carbon atoms, or a perfluoropolyether group having 3 to 30 carbon atoms; and X is a divalent organic group. x1' is an integer of 3≦x1'≦5;x2' and x3' are integers of 0≦x2'+x3'≦20;y1' is an integer of 0≦y1'≦30;y2' is an integer of 0≦y2'≦30;z1' is an integer of 0≦z1'≦10;z2' is an integer of 0≦z2'≦10; and w is 0<w≦10, with the proviso that x2', x3', y1', y2', z1', and z2' are not simultaneously 0.)
The organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
（Ｂ’）成分であるオルガノハイドロジェンポリシロキサンは、下記式（２Ａ）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサンである。 (B') Organohydrogenpolysiloxane The organohydrogenpolysiloxane of the component (B') is represented by the following formula (2A):
The organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
上記式（２Ａ）においてｗは０＜ｗ≦１０であるため、（Ｂ’）成分であるオルガノハイドロジェンポリシロキサンは、「ＳｉＯ４／２」単位、すなわちＱ単位を必ず含む。
In the above formula (2A), w satisfies 0<w≦10, and therefore the organohydrogenpolysiloxane which is component (B′) necessarily contains “SiO 4/2 ” units, that is, Q units.
該オルガノハイドロジェンポリシロキサンは、（Ａ’）成分とヒドロシリル化付加反応し、硬化剤（架橋剤）として作用する。
The organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A') and acts as a curing agent (crosslinking agent).
（Ｂ’）成分の分子構造は、末端ハイドロジェン変性の分岐状シロキサンが好ましく、該オルガノハイドロジェンシロキサンを含むことにより、そのシリコーンゴム硬化物は速硬化、高強度化することが可能になる。
The molecular structure of component (B') is preferably a branched siloxane modified with terminal hydrogen, and by including this organohydrogensiloxane, the silicone rubber cured product can be cured quickly and with high strength.
（Ｂ’）成分であるオルガノハイドロジェンポリシロキサンは、好ましくは、下記式（２Ａ’）
（上記式（２Ａ’）中、Ｒ４は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、または炭素数７～１２のアラルキル基から選ばれる基であり、Ｘは２価の有機基である。ｘ１’は３≦ｘ１’≦５の整数であり、ｘ２’及びｘ３’は０≦ｘ２’＋ｘ３’≦２０の整数であり、ｙ１’は０≦ｙ１’≦３０の整数であり、ｙ２’は０≦ｙ２’≦３０の整数であり、ｗは０＜ｗ≦１０であり、ｋは１～１０の整数であり、ただし、ｘ２’、ｘ３’、ｙ１’及びｙ２’は同時に０とならない。）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサンである。 The organohydrogenpolysiloxane of component (B') is preferably represented by the following formula (2A'):
(In the above formula (2A'), R4 's are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and X is a divalent organic group. x1' is an integer of 3≦x1'≦5, x2' and x3' are integers of 0≦x2'+x3'≦20, y1' is an integer of 0≦y1'≦30, y2' is an integer of 0≦y2'≦30, w is 0<w≦10, and k is an integer of 1 to 10, with the proviso that x2', x3', y1', and y2' are not all 0 at the same time.)
The organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサンである。 The organohydrogenpolysiloxane of component (B') is preferably represented by the following formula (2A'):
The organohydrogenpolysiloxane has 3 to 5 silicon-bonded hydrogen atoms per molecule, and is represented by the following formula:
ケイ素原子に結合した水素原子以外のケイ素原子に結合する１価の有機基Ｒ４としては、炭素数１～８、好ましくは炭素数１～６の、非置換又は置換の、アルケニル基等の脂肪族不飽和結合を含有しない１価炭化水素基であるアルキル基、炭素数６～１２の、脂肪族不飽和結合を含有しないアリール基、及び炭素数７～１２の、脂肪族不飽和結合を含有しないアラルキル基が例示できる。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基が挙げられ、好ましくはメチル基である。
Examples of monovalent organic groups R4 bonded to silicon atoms other than hydrogen atoms bonded to silicon atoms include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which are unsubstituted or substituted monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, such as alkenyl groups, aryl groups having 6 to 12 carbon atoms that do not contain aliphatic unsaturated bonds, and aralkyl groups having 7 to 12 carbon atoms that do not contain aliphatic unsaturated bonds. Examples of such groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, cyclohexyl groups, octyl groups, nonyl groups, and decyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups, and aralkyl groups such as benzyl groups, phenylethyl groups, and phenylpropyl groups, with methyl groups being preferred.
（Ｂ’）成分の１分子中のケイ素原子の数（又は重合度）は、好ましくは４～６０個、より好ましくは４～５０個、更に好ましくは４～４０個である。
The number of silicon atoms (or degree of polymerization) in one molecule of component (B') is preferably 4 to 60, more preferably 4 to 50, and even more preferably 4 to 40.
ケイ素原子に結合した水素原子以外のケイ素原子に結合する１価の有機基Ｒｆ’は、炭素数１～１０のパーフルオロアルキル基、３～３０のパーフルオロポリエーテル基であり、好ましくはパーフルオロアルキル基であり、より好ましくは３，３，３－トリフルオロプロピル基である。
The monovalent organic group Rf' bonded to a silicon atom other than a hydrogen atom bonded to the silicon atom is a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoropolyether group having 3 to 30 carbon atoms, preferably a perfluoroalkyl group, and more preferably a 3,3,3-trifluoropropyl group.
（Ｂ’）成分は室温（２５℃）で液状であるのがよい。該（Ｂ’）成分の２５℃における粘度は０．１～１，０００ｍＰａ・ｓであることが好ましく、より好ましくは０．５～５００ｍＰａ・ｓ、更に好ましくは１～２００ｍＰａ・ｓである。２５℃における粘度が０．１～１，０００ｍＰａ・ｓであれば、良好な作業性を示すことができる。
Component (B') should be liquid at room temperature (25°C). The viscosity of component (B') at 25°C is preferably 0.1 to 1,000 mPa·s, more preferably 0.5 to 500 mPa·s, and even more preferably 1 to 200 mPa·s. If the viscosity at 25°C is 0.1 to 1,000 mPa·s, good workability can be achieved.
（Ｂ’）成分の量は、本発明の第２態様の組成物中のケイ素原子結合アルケニル基１個に対して（Ｂ’）成分中のケイ素原子結合水素原子の個数比が０．５～１０個、好ましくは１～５個の範囲内となる量である。（Ｂ’）成分の量が上記下限値未満であると、得られる組成物は十分に硬化しない。また、（Ｂ’）成分の配合量が上記上限値を超えると、得られるシリコーンゴムの耐熱性が極端に劣ったものとなる。尚、後述する（Ａ’）成分以外のアルケニル基含有オルガノシロキサンを含む場合は、組成物中のケイ素原子に結合するアルケニル基の個数に対する、該（Ｂ’）成分のケイ素原子結合水素原子の個数比が上記範囲を満たせばよい。
The amount of component (B') is such that the ratio of the number of silicon-bonded hydrogen atoms in component (B') to one silicon-bonded alkenyl group in the composition of the second embodiment of the present invention is within the range of 0.5 to 10, preferably 1 to 5. If the amount of component (B') is less than the above lower limit, the resulting composition will not cure sufficiently. If the amount of component (B') exceeds the above upper limit, the heat resistance of the resulting silicone rubber will be extremely poor. Note that, when an alkenyl-containing organosiloxane other than component (A') described below is included, it is sufficient that the ratio of the number of silicon-bonded hydrogen atoms in component (B') to the number of alkenyl groups bonded to silicon atoms in the composition satisfies the above range.
（Ｂ’）成分は、１種単独で用いてもよいし、２種以上を併用してもよい。また、（Ｂ’）成分は、その他ケイ素原子結合水素原子を１分子中に２個以上有するオルガノハイドロジェンポリシロキサンと二種以上併用してもよい。
The (B') component may be used alone or in combination of two or more types. In addition, the (B') component may be used in combination with two or more types of organohydrogenpolysiloxanes having two or more silicon-bonded hydrogen atoms in each molecule.
（Ｃ’）付加反応触媒
（Ｃ’）成分の付加反応触媒は、（Ａ’）成分中のアルケニル基（ビニル基）と（Ｂ’）成分中のケイ素原子に結合した水素原子との付加反応を促進するものであればいかなる触媒であってもよい。通常は、白金族金属系触媒が好適に使用できる。例えば、白金、パラジウム、ロジウム等や塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサン又はアセチレン化合物との配位化合物、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等の、白金族金属又はそれらの化合物が挙げられるが、特に好ましくは白金系化合物である。 (C') Addition reaction catalyst The addition reaction catalyst of component (C') may be any catalyst that promotes the addition reaction between the alkenyl group (vinyl group) in component (A') and the hydrogen atom bonded to the silicon atom in component (B'). Usually, platinum group metal catalysts are preferably used. For example, platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxane or acetylene compounds, tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., platinum group metals or compounds thereof are listed, and particularly preferred are platinum compounds.
（Ｃ’）成分の付加反応触媒は、（Ａ’）成分中のアルケニル基（ビニル基）と（Ｂ’）成分中のケイ素原子に結合した水素原子との付加反応を促進するものであればいかなる触媒であってもよい。通常は、白金族金属系触媒が好適に使用できる。例えば、白金、パラジウム、ロジウム等や塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサン又はアセチレン化合物との配位化合物、テトラキス（トリフェニルホスフィン）パラジウム、クロロトリス（トリフェニルホスフィン）ロジウム等の、白金族金属又はそれらの化合物が挙げられるが、特に好ましくは白金系化合物である。 (C') Addition reaction catalyst The addition reaction catalyst of component (C') may be any catalyst that promotes the addition reaction between the alkenyl group (vinyl group) in component (A') and the hydrogen atom bonded to the silicon atom in component (B'). Usually, platinum group metal catalysts are preferably used. For example, platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinylsiloxane or acetylene compounds, tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., platinum group metals or compounds thereof are listed, and particularly preferred are platinum compounds.
（Ｃ’）成分は、１種単独で用いても２種以上を併用してもよい。
Component (C') may be used alone or in combination of two or more types.
（Ｃ’）成分の配合量は、触媒としての有効量でよいが、（Ａ’）成分の量に対して、触媒金属元素（白金族金属元素）に換算して質量基準で、通常、０．５～１，０００ｐｐｍ、好ましくは１～５００ｐｐｍの範囲であり、１０～１００ｐｐｍの範囲であることがより好ましい。かかる範囲を満たすと、付加反応の反応速度が適切なものとなり、かつ硬化物の耐熱性が良好なものとなる。
The amount of component (C') to be blended may be an effective amount as a catalyst, but is usually in the range of 0.5 to 1,000 ppm, preferably 1 to 500 ppm, and more preferably 10 to 100 ppm, by mass, converted into catalytic metal element (platinum group metal element) relative to the amount of component (A'). If this range is satisfied, the reaction rate of the addition reaction will be appropriate, and the heat resistance of the cured product will be good.
（Ｄ’）補強性シリカ充填剤
（Ｄ’）成分は、下記式（３Ａ）で表される分子鎖両末端にシラノール基を有する直鎖状有機ケイ素化合物で表面処理した補強性シリカである。
(D') Reinforcing Silica Filler Component (D') is a reinforcing silica that has been surface-treated with a linear organosilicon compound having silanol groups at both molecular chain terminals, represented by the following formula (3A).
（Ｄ’）成分は、下記式（３Ａ）で表される分子鎖両末端にシラノール基を有する直鎖状有機ケイ素化合物で表面処理した補強性シリカである。
上記式（３Ａ）中、Ｒ３は、互いに独立に、炭素数１～８のアルキル基、炭素数６～１２のアリール基、又は炭素数７～１２のアラルキル基から選ばれる基であり、例えば上記Ｒ１のために記載した例示が挙げられる。好ましくはメチル基である。Ｒ２は、互いに独立に、上記Ｒ３で示される基、又は３，３，３－トリフルオロプロピル基であり、ただし、Ｒ２の少なくとも１個は３，３，３－トリフルオロプロピル基である。ｐは１≦ｐ≦２０の整数であり、好ましくは３～９の整数である。
In the above formula (3A), R 3 is, independently of each other, a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and examples thereof include those described above for R 1. A methyl group is preferable. R 2 is, independently of each other, a group represented by R 3 above, or a 3,3,3-trifluoropropyl group, with the proviso that at least one of R 2 is a 3,3,3-trifluoropropyl group. p is an integer satisfying 1≦p≦20, and is preferably an integer from 3 to 9.
本発明の第２態様において該補強性シリカ充填剤は、得られるシリコーンゴムに機械的強度を与えるために必須である。上記式（３Ａ）で表される有機ケイ素化合物が３，３，３－トリフルオロプロピル基を有さないと、得られる硬化物は引張強さ、切断時伸びや圧縮永久ひずみなどが劣る。
In the second aspect of the present invention, the reinforcing silica filler is essential for imparting mechanical strength to the resulting silicone rubber. If the organosilicon compound represented by the above formula (3A) does not have a 3,3,3-trifluoropropyl group, the resulting cured product will have inferior tensile strength, elongation at break, compression set, etc.
上記分子鎖両末端がシラノール基で封鎖された直鎖状有機ケイ素化合物で表面処理された補強性シリカ充填剤を含有することで、本組成物の粘度及び加熱硬化後のゴムの圧縮永久ひずみを低くすることができる。
By containing the reinforcing silica filler, which has been surface-treated with a linear organosilicon compound in which both ends of the molecular chain are blocked with silanol groups, it is possible to reduce the viscosity of the composition and the compression set of the rubber after heat curing.
上記補強性シリカ充填剤としては、従来からシリコーンゴム組成物に使用されているものを用いることができ、沈澱シリカ（湿式シリカ）、ヒュームドシリカ（乾式シリカ）、焼成シリカ等が好適である。特にはヒュームドシリカが好適である。
The reinforcing silica filler may be any of those conventionally used in silicone rubber compositions, with precipitated silica (wet silica), fumed silica (dry silica), calcined silica, etc. being preferred. Fumed silica is particularly preferred.
（Ｄ’）成分は、表面未処理のシリカを予め上記式（３Ａ）の有機ケイ素化合物で表面処理したものでよい。あるいは、表面未処理のシリカとポリシロキサン分（すなわち（Ａ’）成分）とを混練し、上記式（３Ａ）の有機ケイ素化合物を添加して、好ましくは少量の水の存在下に、加熱混合して混合物中で表面処理してもよい。また、好ましくは本発明の第２態様で用いる表面未処理のシリカとは、ジメチルジクロロシラン等で表面処理された乾式シリカ（例えば、アエロジルＲ－９７４等）であってもよい。このようにジメチルジクロロシラン等で表面処理された乾式シリカの表面を、上記式（３Ａ）有機ケイ素化合物でさらに処理するのが好ましい。
The (D') component may be surface-untreated silica that has been previously surface-treated with the organosilicon compound of formula (3A). Alternatively, the surface-untreated silica may be kneaded with a polysiloxane component (i.e., component (A')), and the organosilicon compound of formula (3A) may be added, and the mixture may be heated and mixed, preferably in the presence of a small amount of water, to perform surface treatment in the mixture. The surface-untreated silica used in the second aspect of the present invention may preferably be dry silica (e.g., Aerosil R-974, etc.) that has been surface-treated with dimethyldichlorosilane or the like. It is preferable to further treat the surface of the dry silica that has been surface-treated with dimethyldichlorosilane or the like in this way with the organosilicon compound of formula (3A).
上記式（３Ａ）の有機ケイ素化合物によりシリカを表面処理する際の処理量は、上記式（３Ａ）の有機ケイ素化合物で表面処理する前のシリカ４０質量部に対して上記式（３Ａ）の有機ケイ素化合物を１～３０質量部、特に２～２０質量部で表面処理することが好ましい。
When surface treating silica with the organosilicon compound of formula (3A), the amount of the organosilicon compound of formula (3A) is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 40 parts by mass of silica prior to surface treatment with the organosilicon compound of formula (3A).
また、上記式（３Ａ）の有機ケイ素化合物以外の、オルガノシランやオルガノシラザンを表面処理剤として併用してもよい。オルガノシランの例としては、トリメチルクロロシラン、ジメチルジクロロシラン、ジメチルビニルクロロシラン、トリビニルクロロシランなどのクロロシラン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス（メトキシエトキシ）シラン、などのアルコキシシラン類、ヘキサメチルジシラザン、ヘキサメチルシクロトリシラザン、１，３－ジビニル－１，１，３，３－テトラメチルジシラザンなどのシラザン類などが挙げられ、中でも、ヘキサメチルジシラザン、１，３－ジビニル－１，１，３，３－テトラメチルジシラザンなどが好ましい。これらのオルガノシランやオルガノシラザンの処理量は、表面未処理のシリカ４０質量部に対して０．１～１５質量部、特に０．１～１０質量部で表面処理することが好ましい。
In addition, organosilanes and organosilazanes other than the organosilicon compound of the above formula (3A) may be used in combination as a surface treatment agent. Examples of organosilanes include chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, and trivinylchlorosilane, alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, and vinyltris(methoxyethoxy)silane, and silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, and 1,3-divinyl-1,1,3,3-tetramethyldisilazane, among which hexamethyldisilazane and 1,3-divinyl-1,1,3,3-tetramethyldisilazane are preferred. The amount of these organosilanes or organosilazanes used for surface treatment is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 40 parts by mass of untreated silica.
上記式（３Ａ）の有機ケイ素化合物で表面処理する前のシリカのＢＥＴ法による比表面積は、５０ｍ２／ｇ以上、好ましくは１００～４００ｍ２／ｇ、より好ましくは１５０～３５０ｍ２／ｇである。比表面積が５０ｍ２／ｇ以上であれば、十分な強度が得られ、ゴム成形品の外観も良好となる。比表面積が４００ｍ２／ｇ以下であれば、配合が容易である。表面処理後のシリカのＢＥＴ法による比表面積も、上記範囲内にあればよい。
The BET specific surface area of the silica before surface treatment with the organosilicon compound of formula (3A) is 50 m 2 /g or more, preferably 100 to 400 m 2 /g, and more preferably 150 to 350 m 2 /g. If the specific surface area is 50 m 2 /g or more, sufficient strength is obtained and the appearance of the rubber molded product is good. If the specific surface area is 400 m 2 /g or less, compounding is easy. The BET specific surface area of the silica after surface treatment may also be within the above range.
（Ｄ’）成分の配合量は、（Ａ’）成分１００質量部に対し、１０～６０質量部であり、好ましくは１５～５５質量部である。配合量が上記下限値未満では、得られるシリコーンゴムが十分なゴム強度を有さず、また上記上限値を超えると組成物中への配合が困難になる。
The amount of component (D') is 10 to 60 parts by mass, and preferably 15 to 55 parts by mass, per 100 parts by mass of component (A'). If the amount is less than the lower limit, the resulting silicone rubber will not have sufficient rubber strength, and if the amount is more than the upper limit, it will be difficult to incorporate it into the composition.
その他の成分
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、前記（Ａ’）～（Ｄ’）成分以外のその他の成分を必要に応じて含有してもよい。配合量は特に限定されない。 The liquid addition-curable fluorosilicone composition according to the second embodiment of the present invention may contain other components in addition to the above-mentioned components (A') to (D'), as necessary. There are no particular limitations on the amounts added.
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、前記（Ａ’）～（Ｄ’）成分以外のその他の成分を必要に応じて含有してもよい。配合量は特に限定されない。 The liquid addition-curable fluorosilicone composition according to the second embodiment of the present invention may contain other components in addition to the above-mentioned components (A') to (D'), as necessary. There are no particular limitations on the amounts added.
その他の成分とは、例えば、カーボンブラック、導電性亜鉛華、金属粉等の導電剤、窒素含有化合物やアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、酸化鉄、酸化セリウムのような耐熱性付与剤、トリアゾール化合物、ベンゾトリアゾール誘導体等の圧縮永久歪向上剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤、チクソ性付与剤等が挙げられる。本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は１分子中にトリアルコキシ基を３個有するイソシアヌル酸誘導体を含有しないことが好ましい。
Other components include, for example, conductive agents such as carbon black, conductive zinc oxide, and metal powder; hydrosilylation reaction inhibitors such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, and sulfur compounds; heat resistance imparting agents such as iron oxide and cerium oxide; compression set improvers such as triazole compounds and benzotriazole derivatives; internal release agents such as dimethyl silicone oil; adhesive agents; and thixotropy imparting agents. It is preferable that the liquid addition-curable fluorosilicone composition of the second aspect of the present invention does not contain an isocyanuric acid derivative having three trialkoxy groups in one molecule.
［調製方法］
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、例えば、上記（Ａ’）～（Ｄ’）成分、及び必要に応じて各任意成分を、ニーダー、プラネタリーミキサーなどの通常の混合撹拌器、混練器等を用いて上記各成分を均一に混合することにより調製することができる。 [Preparation method]
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention can be prepared, for example, by uniformly mixing the above-mentioned components (A') to (D'), and, if necessary, each optional component, using a conventional mixer/stirrer, kneader, or other such device as a kneader or planetary mixer.
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、例えば、上記（Ａ’）～（Ｄ’）成分、及び必要に応じて各任意成分を、ニーダー、プラネタリーミキサーなどの通常の混合撹拌器、混練器等を用いて上記各成分を均一に混合することにより調製することができる。 [Preparation method]
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention can be prepared, for example, by uniformly mixing the above-mentioned components (A') to (D'), and, if necessary, each optional component, using a conventional mixer/stirrer, kneader, or other such device as a kneader or planetary mixer.
［性状］
本発明の第２態様の組成物は２３℃で液状であることが特徴である。作業性等の点から、２３℃において、せん断速度１０ｓ－１での粘度が１，５００Ｐａ・ｓ以下であることが好ましく、より好ましくは１００～１，２００Ｐａ・ｓ、更に好ましくは２００～１，１００Ｐａ・ｓである。この粘度が１，５００Ｐａ・ｓ以下であれば、注入、圧縮及び射出成形を行う際に材料供給にあまり時間がかからず、高い生産性を提供できる。なお、本発明の第２態様において、上記せん断速度下での粘度の測定は、精密回転式粘度計（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ製）を用いて行ったものである。 [Properties]
The composition according to the second aspect of the present invention is characterized in that it is liquid at 23°C. From the viewpoint of workability and the like, the viscosity at 23°C and a shear rate of 10s -1 is preferably 1,500 Pa·s or less, more preferably 100 to 1,200 Pa·s, and even more preferably 200 to 1,100 Pa·s. If the viscosity is 1,500 Pa·s or less, it does not take much time to supply the material when performing injection, compression, and injection molding, and high productivity can be provided. In the second aspect of the present invention, the viscosity at the above shear rate was measured using a precision rotational viscometer (manufactured by Thermo Fisher Scientific).
本発明の第２態様の組成物は２３℃で液状であることが特徴である。作業性等の点から、２３℃において、せん断速度１０ｓ－１での粘度が１，５００Ｐａ・ｓ以下であることが好ましく、より好ましくは１００～１，２００Ｐａ・ｓ、更に好ましくは２００～１，１００Ｐａ・ｓである。この粘度が１，５００Ｐａ・ｓ以下であれば、注入、圧縮及び射出成形を行う際に材料供給にあまり時間がかからず、高い生産性を提供できる。なお、本発明の第２態様において、上記せん断速度下での粘度の測定は、精密回転式粘度計（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ製）を用いて行ったものである。 [Properties]
The composition according to the second aspect of the present invention is characterized in that it is liquid at 23°C. From the viewpoint of workability and the like, the viscosity at 23°C and a shear rate of 10s -1 is preferably 1,500 Pa·s or less, more preferably 100 to 1,200 Pa·s, and even more preferably 200 to 1,100 Pa·s. If the viscosity is 1,500 Pa·s or less, it does not take much time to supply the material when performing injection, compression, and injection molding, and high productivity can be provided. In the second aspect of the present invention, the viscosity at the above shear rate was measured using a precision rotational viscometer (manufactured by Thermo Fisher Scientific).
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は２液型とすることもできる。この場合、架橋剤としての（Ｂ’）成分と付加反応触媒の（Ｃ’）成分とが同一の組成物（Ａ液又はＢ液）中に混在しないように各成分を適宜分割すればよく、例えば、（Ａ’）成分、（Ｃ’）成分及び（Ｄ’）成分を含有するＡ液と、（Ａ’）成分、（Ｂ’）成分及び（Ｄ’）成分を含有するＢ液とからなる２液型の組成物とすることができ、等質量又は等容量で混合できるように調製することが好ましい。
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention can also be a two-liquid type. In this case, each component can be appropriately divided so that the crosslinking agent (B') and the addition reaction catalyst (C') are not mixed in the same composition (Liquid A or Liquid B). For example, a two-liquid type composition can be made consisting of Liquid A containing components (A'), (C'), and (D') and Liquid B containing components (A'), (B'), and (D'), and it is preferable to prepare it so that it can be mixed in equal masses or volumes.
［フルオロシリコーンゴム］
フルオロシリコーンゴムは、本発明の第２態様の付加硬化型フルオロシリコーン組成物の硬化物である。 [Fluorosilicone rubber]
The fluorosilicone rubber is a cured product of the addition-curable fluorosilicone composition according to the second aspect of the present invention.
フルオロシリコーンゴムは、本発明の第２態様の付加硬化型フルオロシリコーン組成物の硬化物である。 [Fluorosilicone rubber]
The fluorosilicone rubber is a cured product of the addition-curable fluorosilicone composition according to the second aspect of the present invention.
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形、射出成形等各種の成形方法に適用することができる。以下、注入成形、圧縮成形、又は射出成形によるフルオロシリコーンゴムの成形方法について詳細に説明する。
The liquid addition-curable fluorosilicone composition of the second aspect of the present invention can be applied to various molding methods such as injection molding, compression molding, and injection molding. Below, the molding method of fluorosilicone rubber by injection molding, compression molding, or injection molding will be explained in detail.
注入成形の場合、液状付加硬化型フルオロシリコーン組成物は、Ａ液とＢ液との２液型に分割される。２液に分割された材料（成分）は、各Ａ液及びＢ液を等量混合し、金属金型内に注入され、恒温槽で加熱されて硬化し、シリコーンゴムが成形される。
In the case of injection molding, the liquid addition-curing fluorosilicone composition is divided into two liquids, liquid A and liquid B. The two liquid materials (components) are mixed in equal amounts and injected into a metal mold, where they are heated in a thermostatic bath to harden and form silicone rubber.
圧縮成形の場合、プレス機などの圧縮機に金属金型を設置し、注入成形と同様に上記Ａ液及びＢ液を等量混合し、金型に注入され、加熱されて硬化し、シリコーンゴムが成形される。
In the case of compression molding, a metal mold is placed on a compressor such as a press, and equal amounts of the above liquids A and B are mixed in the same way as in injection molding, and then injected into the mold, where it is heated to harden and form the silicone rubber.
射出成形の場合、各Ａ液及びＢ液が材料供給ポンプから定量器に供給される。定量器からＡ液とＢ液が等量の割合で材料供給ラインを通じて合流する。材料は成形機本体のスクリュー部とシリンダー部で混合される。その後、金型に射出され、金型内で加熱されて硬化し、シリコーンゴムが成形される。
In the case of injection molding, liquid A and liquid B are supplied to a metering machine from a material supply pump. From the metering machine, liquid A and liquid B join together in equal amounts through a material supply line. The materials are mixed in the screw and cylinder sections of the molding machine body. They are then injected into a mold, where they are heated and hardened to form silicone rubber.
液状付加硬化型フルオロシリコーン組成物の硬化成形（１次キュア）条件としては、公知の付加反応硬化型シリコーン組成物と同様でよく、硬化温度は８０～２２０℃、特に１２０～２００℃で、硬化時間は３秒～１０分間、特に５秒～５分間加熱することにより硬化成形することができる。成形した硬化物は、必要に応じて、例えば、１８０～２２０℃で３０分～６時間程度、ポストキュア（２次硬化）させてもよい。
The conditions for hardening and molding (primary cure) of the liquid addition-curing fluorosilicone composition may be the same as those for known addition-reaction-curing silicone compositions, and the composition can be hardened and molded by heating at a hardening temperature of 80-220°C, particularly 120-200°C, and for a hardening time of 3 seconds to 10 minutes, particularly 5 seconds to 5 minutes. If necessary, the molded cured product may be post-cured (secondary cure), for example, at 180-220°C for about 30 minutes to 6 hours.
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物から得られる硬化物（シリコーンゴム）、すなわち本発明の第２態様のシリコーンゴムは、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき測定される、１８０℃２２時間圧縮後の圧縮永久ひずみが１０％以下であり得、機械的強度の引張強さが５．０ＭＰａ以上であり得る。または、ＪＩＳ Ｋ ６２４９：２００３に基づく、圧縮率２５％にて１８０℃で２２時間圧縮後の圧縮永久ひずみが１５％以下であり得、好ましくは１０％以下となるのがよい。圧縮永久ひずみが１０％以下の場合、硬化物は、シール材、Ｏ－ｒｉｎｇ、又はパッキンなどの部品（成型体）として使用できる。機械的強度はゴム成形品の実用強度の点から、引張強さが４．５ＭＰａ以上が好ましく、より好ましくは５．０ＭＰａ以上であるのがよい。
The cured product (silicone rubber) obtained from the liquid addition-curable fluorosilicone composition of the second aspect of the present invention, i.e., the silicone rubber of the second aspect of the present invention, may have a compression set of 10% or less after 22 hours of compression at 180°C, as measured according to the description of JIS K 6249:2003, and a tensile strength of 5.0 MPa or more as mechanical strength. Alternatively, the compression set of the cured product may be 15% or less, and preferably 10% or less, as measured according to JIS K 6249:2003, after 22 hours of compression at 180°C with a compression ratio of 25%. When the compression set is 10% or less, the cured product can be used as a part (molded body) such as a sealing material, O-ring, or packing. From the viewpoint of practical strength of rubber molded products, the mechanical strength is preferably 4.5 MPa or more in tensile strength, and more preferably 5.0 MPa or more.
本発明の第２態様の液状付加硬化型フルオロシリコーン組成物を加熱硬化して得られたフルオロシリコーンゴム成形品（シリコーンゴム）は、耐ガソリン性、耐油性に優れることから、航空機や車載用ゴム部品、プリンター部品等又、近年、皮脂耐性の点からモバイル部品や耐酸性の点から燃料電池車用シール部品にも好適に用いることができる。
The fluorosilicone rubber molded product (silicone rubber) obtained by heat curing the liquid addition-curable fluorosilicone composition of the second aspect of the present invention has excellent gasoline and oil resistance, and can therefore be suitably used for aircraft and automotive rubber parts, printer parts, etc. In recent years, it has also been suitable for use in mobile parts due to its sebum resistance, and sealing parts for fuel cell vehicles due to its acid resistance.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。
The present invention will be explained in more detail below with examples and comparative examples, but the present invention is not limited to the following examples.
なお、（Ａ）成分及び（Ａ’）成分の粘度は、２５℃においてＢＨ型回転粘度計（ロータＮｏ．７、回転数１０ｒｐｍ）により測定した。
The viscosities of components (A) and (A') were measured at 25°C using a BH type rotational viscometer (rotor No. 7, rotation speed 10 rpm).
組成物の硬化性は、硬化性試験機［ローターレスタイプディスクレオメータ、ムービングダイ式レオメーター、又はＭＤＲ］による１３０℃で３分測定時の１０％、９０％硬化時間（即ち、１３０℃において測定開始から３分間における最大トルク値に対する１０％、９０％のトルク値を与える時の測定開始からの時間）をＴ１０、Ｔ９０（秒）とし、測定した。
The curability of the composition was measured using a curability tester [rotorless disc rheometer, moving die rheometer, or MDR] at 130°C for 3 minutes, with the 10% and 90% curing times (i.e., the time from the start of measurement at 130°C to give 10% and 90% torque values of the maximum torque value in 3 minutes from the start of measurement) defined as T10 and T90 (seconds).
硬化物の硬さ、引張強さ、切断時伸び、及び引裂強さ（アングル）の測定は以下の方法にて行った。
組成物を１５０℃／１０分のプレスキュアを行ったものに更に２００℃／４時間、恒温槽で２次加硫（ポストキュア）した。得られた硬化物について、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき、硬さ（タイプＡデュロメータ硬さ）、引張強さ、切断時伸び、及び引裂強さ（アングル）を測定した。 The hardness, tensile strength, elongation at break, and tear strength (angle) of the cured product were measured by the following methods.
The composition was press-cured at 150° C. for 10 minutes and then post-cured in a thermostatic chamber at 200° C. for 4 hours. The hardness (type A durometer hardness), tensile strength, elongation at break, and tear strength (angle) of the resulting cured product were measured according to the specifications of JIS K 6249:2003.
組成物を１５０℃／１０分のプレスキュアを行ったものに更に２００℃／４時間、恒温槽で２次加硫（ポストキュア）した。得られた硬化物について、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき、硬さ（タイプＡデュロメータ硬さ）、引張強さ、切断時伸び、及び引裂強さ（アングル）を測定した。 The hardness, tensile strength, elongation at break, and tear strength (angle) of the cured product were measured by the following methods.
The composition was press-cured at 150° C. for 10 minutes and then post-cured in a thermostatic chamber at 200° C. for 4 hours. The hardness (type A durometer hardness), tensile strength, elongation at break, and tear strength (angle) of the resulting cured product were measured according to the specifications of JIS K 6249:2003.
硬化物の圧縮永久ひずみの測定は以下の方法にて行った。
組成物を１５０℃／１５分にて硬化（プレスキュア）し、更に２００℃／４時間、恒温槽で２次加硫（ポストキュア）した。得られた硬化物について、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき圧縮率２５％で１８０℃×２２時間圧縮後の圧縮永久ひずみを測定した。 The compression set of the cured product was measured by the following method.
The composition was cured (press cured) at 150° C. for 15 minutes, and then secondary vulcanized (post cured) in a thermostatic chamber at 200° C. for 4 hours. The compression set of the resulting cured product was measured after compression at 180° C. for 22 hours at a compression ratio of 25% according to the description of JIS K 6249:2003.
組成物を１５０℃／１５分にて硬化（プレスキュア）し、更に２００℃／４時間、恒温槽で２次加硫（ポストキュア）した。得られた硬化物について、ＪＩＳ Ｋ ６２４９：２００３の記載に基づき圧縮率２５％で１８０℃×２２時間圧縮後の圧縮永久ひずみを測定した。 The compression set of the cured product was measured by the following method.
The composition was cured (press cured) at 150° C. for 15 minutes, and then secondary vulcanized (post cured) in a thermostatic chamber at 200° C. for 4 hours. The compression set of the resulting cured product was measured after compression at 180° C. for 22 hours at a compression ratio of 25% according to the description of JIS K 6249:2003.
＜実施例１～４、並びに比較例１及び２＞
下記実施例１～４、並びに比較例１及び２で使用した各成分は以下の通りである。
（Ａ）成分：下記式（４）
で示される両末端がジメチルビニルシロキシ基で封鎖された２５℃の粘度が７６．６Ｐａ・ｓであるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量：４．６×１０－５ｍｏｌ／ｇ］
<Examples 1 to 4 and Comparative Examples 1 and 2>
The components used in the following Examples 1 to 4 and Comparative Examples 1 and 2 are as follows.
Component (A): Formula (4) below
Trifluoropropylmethylpolysiloxane having a viscosity of 76.6 Pa·s at 25° C. and both ends capped with dimethylvinylsiloxy groups [vinyl group content: 4.6×10 −5 mol/g]
下記実施例１～４、並びに比較例１及び２で使用した各成分は以下の通りである。
（Ａ）成分：下記式（４）
The components used in the following Examples 1 to 4 and Comparative Examples 1 and 2 are as follows.
Component (A): Formula (4) below
（Ｄ）成分：ＢＥＴ法による比表面積が２００ｍ２／ｇであるヒュームドシリカ（日本アエロジル社製、アエロジルＲ－９７４）と、
下記式（５）で示される有機ケイ素化合物
Component (D): fumed silica having a specific surface area of 200 m 2 /g as measured by the BET method (Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.);
An organosilicon compound represented by the following formula (5):
下記式（５）で示される有機ケイ素化合物
An organosilicon compound represented by the following formula (5):
（Ｂ）架橋剤：
（Ｂ－１）下記式（６―１）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００８６ｍｏｌ／ｇ］
（Ｂ－２）下記式（６―２）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００２０ｍｏｌ／ｇ］
（Ｂ－３）下記式（６―３）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００１６ｍｏｌ／ｇ］
（Ｂ－４）下記式（６－４）で示されるメチルハイドロジェンポリシロキサン［粘度：０．０６Ｐａ・ｓ、ＳｉＨ基量：０．００４９ｍｏｌ／ｇ］
(B) Crosslinking agent:
(B-1) Methylhydrogenpolysiloxane represented by the following formula (6-1) [SiH group amount: 0.0086 mol/g]
(B-2) Methylhydrogenpolysiloxane represented by the following formula (6-2) [SiH group amount: 0.0020 mol/g]
(B-3) Methylhydrogenpolysiloxane represented by the following formula (6-3) [SiH group amount: 0.0016 mol/g]
(B-4) Methylhydrogenpolysiloxane represented by the following formula (6-4) [viscosity: 0.06 Pa·s, SiH group amount: 0.0049 mol/g]
（Ｂ－１）下記式（６―１）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００８６ｍｏｌ／ｇ］
(B-1) Methylhydrogenpolysiloxane represented by the following formula (6-1) [SiH group amount: 0.0086 mol/g]
（Ｃ）白金触媒（Ｐｔ濃度：０．５質量％）
(C) Platinum catalyst (Pt concentration: 0.5% by mass)
（その他の成分）
反応制御剤：エチニルシクロヘキサノール
圧縮永久ひずみ向上剤：下記式（７）で示されるベンゾトリアゾールシラン
耐熱性付与剤：酸化セリウム
(Other ingredients)
Reaction inhibitor: ethynylcyclohexanol Compression set improver: benzotriazole silane represented by the following formula (7)
Heat resistance agent: cerium oxide
反応制御剤：エチニルシクロヘキサノール
圧縮永久ひずみ向上剤：下記式（７）で示されるベンゾトリアゾールシラン
Reaction inhibitor: ethynylcyclohexanol Compression set improver: benzotriazole silane represented by the following formula (7)
［調製例１］
（Ａ）上記式（４）で示されるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量４．６×１０－５ｍｏｌ／ｇ］５５質量部、補強性シリカ充填剤として上記ヒュームドシリカ４０質量部、上記式（５）で示される有機ケイ素化合物６質量部、水０．５質量部、及び、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン０．４質量部を２５℃で３０分混合後、１６０℃に昇温し、３時間攪拌を続けた。さらに上記式（４）で表されるトリフルオロプロピルメチルポリシロキサン６０質量部を添加し、３０分混合後、シリコーンゴムベースＡ１を得た。なお、得られたシリコーンゴムベース中、（Ａ）成分１００質量部あたりの（Ｄ）成分の量は３５質量部である。 [Preparation Example 1]
(A) 55 parts by mass of trifluoropropylmethylpolysiloxane [vinyl group content 4.6×10 −5 mol/g] represented by the above formula (4), 40 parts by mass of the above fumed silica as a reinforcing silica filler, 6 parts by mass of organosilicon compound represented by the above formula (5), 0.5 parts by mass of water, and 0.4 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldisilazane were mixed at 25° C. for 30 minutes, then heated to 160° C. and continued stirring for 3 hours. Further, 60 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4) was added, and after mixing for 30 minutes, silicone rubber base A1 was obtained. In addition, in the obtained silicone rubber base, the amount of component (D) per 100 parts by mass of component (A) was 35 parts by mass.
（Ａ）上記式（４）で示されるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量４．６×１０－５ｍｏｌ／ｇ］５５質量部、補強性シリカ充填剤として上記ヒュームドシリカ４０質量部、上記式（５）で示される有機ケイ素化合物６質量部、水０．５質量部、及び、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン０．４質量部を２５℃で３０分混合後、１６０℃に昇温し、３時間攪拌を続けた。さらに上記式（４）で表されるトリフルオロプロピルメチルポリシロキサン６０質量部を添加し、３０分混合後、シリコーンゴムベースＡ１を得た。なお、得られたシリコーンゴムベース中、（Ａ）成分１００質量部あたりの（Ｄ）成分の量は３５質量部である。 [Preparation Example 1]
(A) 55 parts by mass of trifluoropropylmethylpolysiloxane [vinyl group content 4.6×10 −5 mol/g] represented by the above formula (4), 40 parts by mass of the above fumed silica as a reinforcing silica filler, 6 parts by mass of organosilicon compound represented by the above formula (5), 0.5 parts by mass of water, and 0.4 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldisilazane were mixed at 25° C. for 30 minutes, then heated to 160° C. and continued stirring for 3 hours. Further, 60 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4) was added, and after mixing for 30 minutes, silicone rubber base A1 was obtained. In addition, in the obtained silicone rubber base, the amount of component (D) per 100 parts by mass of component (A) was 35 parts by mass.
［実施例１～４、比較例１，２］
下記表１に示す配合量でシリコーンゴム組成物を調製した。得られた組成物は、上記条件にて粘度を測定し、硬化物を作製して上記一般物性を測定した。これらの結果を表１に記載した。なお、表中の「硬化性Ｔ１０／Ｔ９０」の欄では、上記測定方法により求めた１０％、９０％硬化時間（秒）をそれぞれ示し、「硬化性Ｔ９０－Ｔ１０」の欄ではその差を示した。この差が小さいほど硬化が速い。また、「ＳｉＨ／ＳｉＶｉ」は組成物中のＳｉＶｉ基に対する（Ｂ）成分中のＳｉＨ基の個数比である。 [Examples 1 to 4, Comparative Examples 1 and 2]
A silicone rubber composition was prepared in the amounts shown in Table 1 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the above general physical properties were measured. These results are shown in Table 1. In the table, the "Curability T10/T90" column shows the 10% and 90% curing times (seconds) determined by the above measurement method, and the "Curability T90-T10" column shows the difference between them. The smaller the difference, the faster the curing. Additionally, "SiH/SiVi" is the ratio of the number of SiH groups in component (B) to the number of SiVi groups in the composition.
下記表１に示す配合量でシリコーンゴム組成物を調製した。得られた組成物は、上記条件にて粘度を測定し、硬化物を作製して上記一般物性を測定した。これらの結果を表１に記載した。なお、表中の「硬化性Ｔ１０／Ｔ９０」の欄では、上記測定方法により求めた１０％、９０％硬化時間（秒）をそれぞれ示し、「硬化性Ｔ９０－Ｔ１０」の欄ではその差を示した。この差が小さいほど硬化が速い。また、「ＳｉＨ／ＳｉＶｉ」は組成物中のＳｉＶｉ基に対する（Ｂ）成分中のＳｉＨ基の個数比である。 [Examples 1 to 4, Comparative Examples 1 and 2]
A silicone rubber composition was prepared in the amounts shown in Table 1 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the above general physical properties were measured. These results are shown in Table 1. In the table, the "Curability T10/T90" column shows the 10% and 90% curing times (seconds) determined by the above measurement method, and the "Curability T90-T10" column shows the difference between them. The smaller the difference, the faster the curing. Additionally, "SiH/SiVi" is the ratio of the number of SiH groups in component (B) to the number of SiVi groups in the composition.
上記表１に示す通り、本発明の第１態様の液状付加硬化型フルオロシリコーン組成物から得られる硬化物は硬化性が良く（硬化が速く）、引張強さ、及び切断時伸びに優れる。一方、本発明の第１態様に係る有機ケイ素化合物で側鎖がハイドロジェン変性された直鎖状シリコーン（Ｂ－４）を用いた比較例１、２のフルオロシリコーン組成物では、硬化性が劣り（硬化がやや遅く）、また機械的強度にも劣った。
As shown in Table 1 above, the cured product obtained from the liquid addition-curable fluorosilicone composition of the first embodiment of the present invention has good curability (fast curing) and excellent tensile strength and elongation at break. On the other hand, the fluorosilicone compositions of Comparative Examples 1 and 2, which use linear silicone (B-4) whose side chains are hydrogen-modified with the organosilicon compound according to the first embodiment of the present invention, have poor curability (slightly slow curing) and also have poor mechanical strength.
本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形用材料として好適であり成形品の生産性向上に寄与することができる。また、本発明の第１態様の液状付加硬化型フルオロシリコーン組成物は加熱硬化後の圧縮永久ひずみの値が低く、シール材、Ｏ－ｒｉｎｇ、又はパッキンなどのゴム成形体として好適に使用できる。
The liquid addition-curable fluorosilicone composition of the first aspect of the present invention is suitable as a material for casting, compression molding, and injection molding, and can contribute to improving the productivity of molded products. In addition, the liquid addition-curable fluorosilicone composition of the first aspect of the present invention has a low compression set value after heat curing, and can be suitably used as rubber molded products such as sealing materials, O-rings, and packings.
＜実施例５～８、比較例３＞
実施例５～８、及び比較例３では、組成物の保存安定性は以下の方法で評価した。
組成物を３０℃×３日後、又は３０℃×７日後において、目視確認により流動性を維持し液状であるものを○、ゲル化してしまったものを×とした。 <Examples 5 to 8, Comparative Example 3>
In Examples 5 to 8 and Comparative Example 3, the storage stability of the compositions was evaluated by the following method.
After storing the composition at 30° C. for 3 days or 7 days, the composition was visually inspected to determine whether it maintained fluidity and was liquid, and whether it had gelled, and was evaluated as "good."
実施例５～８、及び比較例３では、組成物の保存安定性は以下の方法で評価した。
組成物を３０℃×３日後、又は３０℃×７日後において、目視確認により流動性を維持し液状であるものを○、ゲル化してしまったものを×とした。 <Examples 5 to 8, Comparative Example 3>
In Examples 5 to 8 and Comparative Example 3, the storage stability of the compositions was evaluated by the following method.
After storing the composition at 30° C. for 3 days or 7 days, the composition was visually inspected to determine whether it maintained fluidity and was liquid, and whether it had gelled, and was evaluated as "good."
下記実施例５～８、及び比較例３で使用した各成分は以下の通りである。
The components used in Examples 5 to 8 and Comparative Example 3 are as follows:
（Ａ’）成分：下記式（４’）
で示される両末端がジメチルビニルシロキシ基で封鎖された２５℃の粘度が７６．６Ｐａ・ｓであるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量：４．６×１０－５ｍｏｌ／ｇ］
Component (A'): Formula (4') below
Trifluoropropylmethylpolysiloxane having a viscosity of 76.6 Pa·s at 25° C. and both ends capped with dimethylvinylsiloxy groups [vinyl group content: 4.6×10 −5 mol/g]
（Ｄ’）成分：ＢＥＴ法による比表面積が２００ｍ２／ｇであるヒュームドシリカ（日本アエロジル社製、アエロジルＲ－９７４）と、
下記式（５’）で示される有機ケイ素化合物
Component (D'): fumed silica having a specific surface area of 200 m 2 /g as measured by the BET method (Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.);
An organosilicon compound represented by the following formula (5'):
下記式（５’）で示される有機ケイ素化合物
An organosilicon compound represented by the following formula (5'):
（Ｂ’）架橋剤：（Ｂ’－１）下記式（６―１’）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．０１２ｍｏｌ／ｇ］
(B') Crosslinking agent: (B'-1) Methylhydrogenpolysiloxane represented by the following formula (6-1') [SiH group amount: 0.012 mol/g]
（Ｂ’－２）下記式（６―２’）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００１８ｍｏｌ／ｇ］
(B'-2) Methylhydrogenpolysiloxane represented by the following formula (6-2') [SiH group amount: 0.0018 mol/g]
（Ｂ’－３）下記式（６―３’）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．００１７ｍｏｌ／ｇ］
(B'-3) Methylhydrogenpolysiloxane represented by the following formula (6-3') [SiH group amount: 0.0017 mol/g]
（Ｂ’－４）下記式（６－４’）で示されるメチルハイドロジェンポリシロキサン［粘度：０．０６Ｐａ・ｓ、ＳｉＨ基量：０．００４９ｍｏｌ／ｇ］
(B'-4) Methylhydrogenpolysiloxane represented by the following formula (6-4') [viscosity: 0.06 Pa·s, SiH group amount: 0.0049 mol/g]
（Ｂ’―５）架橋剤：下記式（６―５’）で示されるメチルハイドロジェンポリシロキサン［ＳｉＨ基量：０．０８６ｍｏｌ／ｇ］
(B'-5) Crosslinking agent: Methylhydrogenpolysiloxane represented by the following formula (6-5') [SiH group amount: 0.086 mol/g]
（Ｃ’）白金触媒（Ｐｔ濃度：０．５質量％）
(C') Platinum catalyst (Pt concentration: 0.5% by mass)
その他の成分：
反応制御剤：エチニルシクロヘキサノール
圧縮永久歪向上剤：下記式（７）で示されるベンゾトリアゾールシラン
耐熱性付与剤：酸化セリウム
Other Ingredients:
Reaction inhibitor: ethynylcyclohexanol Compression set improver: benzotriazole silane represented by the following formula (7)
Heat resistance agent: cerium oxide
反応制御剤：エチニルシクロヘキサノール
圧縮永久歪向上剤：下記式（７）で示されるベンゾトリアゾールシラン
Reaction inhibitor: ethynylcyclohexanol Compression set improver: benzotriazole silane represented by the following formula (7)
［調製例２］
（Ａ’）上記式（４’）で示されるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量４．６×１０－５ｍｏｌ／ｇ］５５質量部、補強性シリカ充填剤として上記ヒュームドシリカ４０質量部、上記式（５’）で示される有機ケイ素化合物６質量部、水０．５質量部、及び、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン０．４質量部を、２５℃で３０分混合後、１６０℃に昇温し、３時間攪拌を続けた。さらに上記式（４’）で表されるトリフルオロプロピルメチルポリシロキサン６０質量部を添加し、３０分混合後、シリコーンゴムベースＡ１’を得た。なお、得られたシリコーンゴムベース中、（Ａ’）成分１００質量部あたりの（Ｄ’）成分の量は３５質量部である。 [Preparation Example 2]
(A') 55 parts by mass of trifluoropropylmethylpolysiloxane [vinyl group content 4.6 x 10 -5 mol/g] represented by the above formula (4'), 40 parts by mass of the above fumed silica as a reinforcing silica filler, 6 parts by mass of organosilicon compound represented by the above formula (5'), 0.5 parts by mass of water, and 0.4 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldisilazane were mixed at 25°C for 30 minutes, then heated to 160°C and stirred for 3 hours. Further, 60 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4') was added, and after mixing for 30 minutes, a silicone rubber base A1' was obtained. In addition, in the obtained silicone rubber base, the amount of component (D') per 100 parts by mass of component (A') was 35 parts by mass.
（Ａ’）上記式（４’）で示されるトリフルオロプロピルメチルポリシロキサン［ビニル基含有量４．６×１０－５ｍｏｌ／ｇ］５５質量部、補強性シリカ充填剤として上記ヒュームドシリカ４０質量部、上記式（５’）で示される有機ケイ素化合物６質量部、水０．５質量部、及び、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン０．４質量部を、２５℃で３０分混合後、１６０℃に昇温し、３時間攪拌を続けた。さらに上記式（４’）で表されるトリフルオロプロピルメチルポリシロキサン６０質量部を添加し、３０分混合後、シリコーンゴムベースＡ１’を得た。なお、得られたシリコーンゴムベース中、（Ａ’）成分１００質量部あたりの（Ｄ’）成分の量は３５質量部である。 [Preparation Example 2]
(A') 55 parts by mass of trifluoropropylmethylpolysiloxane [vinyl group content 4.6 x 10 -5 mol/g] represented by the above formula (4'), 40 parts by mass of the above fumed silica as a reinforcing silica filler, 6 parts by mass of organosilicon compound represented by the above formula (5'), 0.5 parts by mass of water, and 0.4 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldisilazane were mixed at 25°C for 30 minutes, then heated to 160°C and stirred for 3 hours. Further, 60 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4') was added, and after mixing for 30 minutes, a silicone rubber base A1' was obtained. In addition, in the obtained silicone rubber base, the amount of component (D') per 100 parts by mass of component (A') was 35 parts by mass.
［実施例５～８、及び比較例３］
下記表２に示す配合量でシリコーンゴム組成物を調製した。得られた組成物は、上記条件にて粘度を測定し、硬化物を作成して上記一般物性を測定した。これらの結果を表２に記載した。 [Examples 5 to 8 and Comparative Example 3]
A silicone rubber composition was prepared in the amounts shown in Table 2 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the general physical properties described above were measured. The results are shown in Table 2.
下記表２に示す配合量でシリコーンゴム組成物を調製した。得られた組成物は、上記条件にて粘度を測定し、硬化物を作成して上記一般物性を測定した。これらの結果を表２に記載した。 [Examples 5 to 8 and Comparative Example 3]
A silicone rubber composition was prepared in the amounts shown in Table 2 below. The viscosity of the resulting composition was measured under the conditions described above, and a cured product was prepared and the general physical properties described above were measured. The results are shown in Table 2.
上記表２に示す通り、本発明の第２態様の例である実施例５～７の液状付加硬化型フルオロシリコーン組成物は、比較例３及び実施例８の組成物よりも硬化性が非常に速く、これらの組成物の硬化物は、比較例３及び実施例８の組成物の硬化物よりも、引張強さ、及び切断時伸びに優れる。また、本発明の第１態様の例である実施例８の液状付加硬化型フルオロシリコーン組成物は、比較例３の組成物よりは硬化性が速く、この組成物の硬化物は、比較例３の組成物の硬化物よりも、引張強さ、及び切断時伸びに優れる。一方、本発明の第２態様の有機ケイ素化合物で側鎖がハイドロジェン変性され且つＳｉＯ４／２単位を含まないシリコーンを用いた比較例３のフルオロシリコーン組成物では、硬化性がやや遅く、またこれらの組成物の硬化物は機械的強度にも劣った。また、本発明の第１態様及び第２態様の例である実施例５～８の液状付加硬化型フルオロシリコーンゴム組成物は、保存安定性が従来と同等かそれ以上であった。
As shown in Table 2 above, the liquid addition-curable fluorosilicone compositions of Examples 5 to 7, which are examples of the second aspect of the present invention, cure much faster than the compositions of Comparative Example 3 and Example 8, and the cured products of these compositions have better tensile strength and elongation at break than the cured products of the compositions of Comparative Example 3 and Example 8. The liquid addition-curable fluorosilicone composition of Example 8, which is an example of the first aspect of the present invention, cures faster than the composition of Comparative Example 3, and the cured product of this composition has better tensile strength and elongation at break than the cured product of the composition of Comparative Example 3. On the other hand, the fluorosilicone composition of Comparative Example 3, which uses a silicone whose side chains are hydrogen-modified with an organosilicon compound of the second aspect of the present invention and does not contain SiO 4/2 units, cures somewhat slowly, and the cured products of these compositions also have inferior mechanical strength. The liquid addition-curable fluorosilicone rubber compositions of Examples 5 to 8, which are examples of the first and second aspects of the present invention, have storage stability equal to or better than that of conventional compositions.
すなわち、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、注入成形、圧縮成形及び射出成形用材料として好適であり成形品の生産性向上に寄与することができる。また、本発明の第２態様の液状付加硬化型フルオロシリコーン組成物は、加熱硬化後の圧縮永久ひずみの値が低く、シール材、Ｏ－ｒｉｎｇ、又はパッキンなどのゴム成型体として好適に使用できる。
In other words, the liquid addition-curable fluorosilicone composition of the second aspect of the present invention is suitable as a material for casting, compression molding, and injection molding, and can contribute to improving the productivity of molded products. In addition, the liquid addition-curable fluorosilicone composition of the second aspect of the present invention has a low compression set value after heat curing, and can be suitably used as rubber molded products such as sealing materials, O-rings, and packings.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and provides similar effects is included within the technical scope of the present invention.
Claims (5)
- 付加硬化型フルオロシリコーン組成物であって、
（Ａ）下記一般式（１）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるビニル基含有オルガノポリシロキサン、
（Ｂ）ケイ素原子結合水素原子を１分子中に３個以上有する下記式（３）
で示される分岐状オルガノハイドロジェンポリシロキサン：（Ｂ）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合ビニル基１個当たり０．５～１０となる量、
（Ｃ）付加反応触媒：触媒量、及び
（Ｄ）下記一般式（２）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有し、
前記付加硬化型フルオロシリコーン組成物が２３℃で液状であることを特徴とする付加硬化型フルオロシリコーン組成物。 An addition-curable fluorosilicone composition comprising:
(A) a compound represented by the following general formula (1):
a vinyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B) a compound represented by the following formula (3) having three or more silicon-bonded hydrogen atoms in one molecule:
a branched organohydrogenpolysiloxane represented by the formula:
(C) an addition reaction catalyst: a catalytic amount; and (D) a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (2):
The addition-curable fluorosilicone composition is characterized in that the addition-curable fluorosilicone composition is liquid at 23°C. - 請求項１に記載の付加硬化型フルオロシリコーン組成物の硬化物であることを特徴とするフルオロシリコーンゴム。 A fluorosilicone rubber that is a cured product of the addition-curable fluorosilicone composition described in claim 1.
- 請求項２に記載のフルオロシリコーンゴムの成形体であることを特徴とするフルオロシリコーンゴム成形品。 A fluorosilicone rubber molded article, characterized in that it is a molded article of the fluorosilicone rubber described in claim 2.
- 液状付加硬化型フルオロシリコーン組成物であって、
（Ａ’）下記一般式（１Ａ）
で示される、２５℃の粘度が１００～５００，０００ｍＰａ・ｓであるアルケニル基含有オルガノポリシロキサン、
（Ｂ’）下記一般式（２Ａ）
で示される、ケイ素原子結合水素原子を１分子中に３～５個有するオルガノハイドロジェンポリシロキサン：（Ｂ’）成分中のケイ素原子に結合した水素原子の数が前記組成物中のケイ素原子結合アルケニル基１個当たり０．５～１０となる量、
（Ｃ’）付加反応触媒：触媒量、及び
（Ｄ’）下記一般式（３Ａ）で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有するものであることを特徴とする、２３℃で液状である、付加硬化型フルオロシリコーン組成物。 A liquid addition-curable fluorosilicone composition comprising:
(A') a compound represented by the following general formula (1A):
an alkenyl group-containing organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa·s,
(B') a compound represented by the following general formula (2A):
an organohydrogenpolysiloxane having 3 to 5 silicon-bonded hydrogen atoms per molecule, represented by the formula:
(C') an addition reaction catalyst: a catalytic amount; and (D') a reinforcing silica filler surface-treated with an organosilicon compound represented by the following general formula (3A):
- 請求項４記載の付加硬化型フルオロシリコーン組成物の硬化物であることを特徴とするフルオロシリコーンゴム。
5. A fluorosilicone rubber which is a cured product of the addition-curable fluorosilicone composition according to claim 4.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-162686 | 2022-10-07 | ||
| JP2022162686A JP2024055614A (en) | 2022-10-07 | 2022-10-07 | Liquid addition-curable fluorosilicone composition, fluorosilicone rubber and molded article |
| JP2022169054A JP2024061235A (en) | 2022-10-21 | 2022-10-21 | Liquid addition-curable fluorosilicone composition and fluorosilicone rubber |
| JP2022-169054 | 2022-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024075472A1 true WO2024075472A1 (en) | 2024-04-11 |
Family
ID=90607803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/032998 WO2024075472A1 (en) | 2022-10-07 | 2023-09-11 | Liquid addition-curable fluorosilicone composition, fluorosilicone rubber, and molded article |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024075472A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014020920A1 (en) * | 2012-08-02 | 2014-02-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
| JP2016503108A (en) * | 2012-12-28 | 2016-02-01 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Curable organopolysiloxane composition for transducer and use of such curable silicone composition in transducer |
| WO2017183541A1 (en) * | 2016-04-22 | 2017-10-26 | 東レ・ダウコーニング株式会社 | Highly dielectric film, usages thereof, and manufacturing method therefor |
| WO2019026401A1 (en) * | 2017-08-01 | 2019-02-07 | 信越化学工業株式会社 | Silicone rubber composition |
| CN111808430A (en) * | 2020-08-24 | 2020-10-23 | 浙江新安化工集团股份有限公司 | Fluorosilicone rubber compound and preparation method thereof |
| CN113025059A (en) * | 2021-03-09 | 2021-06-25 | 威海新元化工有限公司 | High-tear-strength addition type liquid fluorosilicone rubber and preparation method thereof |
| JP2022172732A (en) * | 2021-05-07 | 2022-11-17 | 信越化学工業株式会社 | Fluorosilicone rubber composition and cured molded product |
-
2023
- 2023-09-11 WO PCT/JP2023/032998 patent/WO2024075472A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014020920A1 (en) * | 2012-08-02 | 2014-02-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
| JP2016503108A (en) * | 2012-12-28 | 2016-02-01 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Curable organopolysiloxane composition for transducer and use of such curable silicone composition in transducer |
| WO2017183541A1 (en) * | 2016-04-22 | 2017-10-26 | 東レ・ダウコーニング株式会社 | Highly dielectric film, usages thereof, and manufacturing method therefor |
| WO2019026401A1 (en) * | 2017-08-01 | 2019-02-07 | 信越化学工業株式会社 | Silicone rubber composition |
| CN111808430A (en) * | 2020-08-24 | 2020-10-23 | 浙江新安化工集团股份有限公司 | Fluorosilicone rubber compound and preparation method thereof |
| CN113025059A (en) * | 2021-03-09 | 2021-06-25 | 威海新元化工有限公司 | High-tear-strength addition type liquid fluorosilicone rubber and preparation method thereof |
| JP2022172732A (en) * | 2021-05-07 | 2022-11-17 | 信越化学工業株式会社 | Fluorosilicone rubber composition and cured molded product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108779336B (en) | Addition-curable silicone rubber composition and cured product | |
| JP6572634B2 (en) | Addition-curable silicone rubber composition and cured product | |
| WO2019031245A1 (en) | Addition-curable silicone composition and cured silicone rubber | |
| JP2013047290A (en) | Liquid addition curable fluorosilicone rubber composition and molded product thereof | |
| JPH02180963A (en) | Organopolysiloxane composition | |
| JP2741436B2 (en) | Surface-treated alumina and thermally conductive silicone composition containing the same | |
| CN113015775B (en) | Adhesive polyorganosiloxane composition | |
| JP5910210B2 (en) | Fluorosilicone rubber composition, integral molded body composed of fluorosilicone rubber layer and thermoplastic resin layer, and method for producing the integral molded body | |
| JP4553562B2 (en) | Adhesive polyorganosiloxane composition | |
| WO2024075472A1 (en) | Liquid addition-curable fluorosilicone composition, fluorosilicone rubber, and molded article | |
| JP5014532B2 (en) | Method for producing liquid addition-curable silicone rubber composition | |
| JP2024055614A (en) | Liquid addition-curable fluorosilicone composition, fluorosilicone rubber and molded article | |
| WO2021241036A1 (en) | Two-pack type addition curable silicone rubber composition | |
| JP7503030B2 (en) | Liquid addition-curable fluorosilicone composition, silicone rubber, molded products | |
| JP2024061235A (en) | Liquid addition-curable fluorosilicone composition and fluorosilicone rubber | |
| JP6108015B2 (en) | Method for reducing modulus of cured silicone rubber, and silicone rubber composition | |
| JP2005060549A (en) | Definite-form adhesive | |
| JP2015017198A (en) | Method for lowering modulus of silicone rubber cured product, silicone rubber composition, and cured product | |
| JP7475791B2 (en) | Method for producing addition-curable silicone composition | |
| KR102676450B1 (en) | Addition-curable silicone rubber compositions and cured products | |
| JP6690737B2 (en) | Novel arylene group-containing organopolysiloxane and curable organopolysiloxane composition using the same | |
| JP2023019548A (en) | Addition-curable fluorosilicone composition, silicone rubber, and molded body | |
| JP2008150445A (en) | Method for producing liquid silicone rubber base, addition curing type liquid silicone rubber composition and silicone rubber cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23874601 Country of ref document: EP Kind code of ref document: A1 |